Methods and compositions using calcium carbonate and stabilizer

ABSTRACT

Provided herein are compositions, methods, and systems for a material containing metastable carbonate and stabilizer. Methods for making the compositions and using the compositions are also provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.61/480,018, filed Apr. 28, 2011; U.S. Provisional Application No.61/526,751, filed Aug. 24, 2011; and U.S. Provisional Application No.61/534,972, filed Sep. 15, 2011, all of which are incorporated herein byreference in their entireties.

GOVERNMENT SUPPORT

Work described herein was made in whole or in part with Governmentsupport under Award Number: DE-FE0002472 awarded by the Department ofEnergy. The Government has certain rights in this invention.

BACKGROUND

Calcium carbonates are used in numerous industries from papermaking, toadhesives production, to construction. Calcium carbonates that areformed as a result of a carbon dioxide sequestering process can be usedin many of the aforementioned applications and in effect can serve twopurposes: to sequester carbon dioxide and to function as a calciumcarbonate material. One area where this dual purpose may be doublybeneficial to the environment is in construction materials, specificallycements and concretes. As the production of conventional cements may beone of the contributors to the emission of carbon dioxide into theatmosphere through the calcination of conventional cements as well asthe energy needed to heat the kilns, reductions in the amount ofconventional cements used can help to reduce the amount of carbondioxide in the earth's atmosphere.

SUMMARY

In one aspect, there is provided a composition, comprising a metastablecarbonate and a stabilizer. In some embodiments, the composition is acementitious composition. In some embodiments, the cementitiouscomposition is a hydraulic cement composition, supplementarycementitious material, self-cementing composition, or combinationthereof. In some embodiments, the metastable carbonate is a calciumcarbonate. In some embodiments, the metastable carbonate is selectedfrom the group consisting of vaterite, amorphous calcium carbonate,aragonite, a precursor phase of vaterite, a precursor phase ofaragonite, an intermediary phase that is less stable than calcite,polymorphic forms in between these polymorphs, and combination thereof.In some embodiments, the metastable carbonate comprises vaterite. Insome embodiments, the metastable carbonate comprises at least 10% w/wvaterite. In some embodiments, the metastable carbonate comprises atleast 10% w/w vaterite and at least 1% w/w amorphous calcium carbonate(ACC). In some embodiments, the metastable carbonate comprises between10-99% w/w or between 10-100% w/w vaterite. In some embodiments, themetastable carbonate comprises at least 50% w/w vaterite. In someembodiments, the metastable carbonate comprises between 50-100% w/wvaterite. In some embodiments, the metastable carbonate comprisesactivated vaterite.

In some embodiments of the foregoing aspects and embodiments, thestabilizer includes, but not limited to, acid, ester, phosphate,sulfate, polyethylene oxide, polyalcohol, and combination thereof. Insome embodiments, the acid is C₁-C₂₀ acid, sulfonic acid, or aphosphonic acid. In some embodiments, the C₁-C₂₀ acid includes, but notlimited to, citric acid, malic acid, adipic acid, tannic acid, lacticacid, ascorbic acid, acetic acid, fumaric acid, and mixtures thereof. Insome embodiments, the sulfonic acid is copolymer of2-acrylamido-2-methyl propanesulfonic acid with acrylic acid. In someembodiments, the phosphonic includes, but not limited to, N-nitrilotris(methylene phosphonic acid), 1,2-ethanediylbis(nitrilo di(methylenephosphonic acid)); 1,6-hexanediylbis(nitrilodi(methylene phosphonicacid)), amino tris(methylene phosphonic acid), polymethoxypolyphosphonic acid, ethylenediamine tetra(methylene phosphonic acid)(EDTMP), and combination thereof. In some embodiments, the acid furthercomprises hydroxyl and/or amino group. In some embodiments, the ester isan ester of a C₁-C₂₀ acid, a phosphonic acid, or a sulfonic acid. Insome embodiments, the ester is an ester of a C₁-C₂₀ acid including, butnot limited to, citric acid, malic acid, adipic acid, tannic acid,lactic acid, ascorbic acid, acetic acid, fumaric acid and mixturesthereof. In some embodiments, the sulfate is in sea water, an alkalimetal sulfate, alkaline earth metal sulfate, lignosulfate, orcombination thereof. In some embodiments, the sulfate is an alkali metalsulfate and/or alkaline earth metal sulfate. In some embodiments, thepolyethylene oxide has a molecular weight of between 1,000 and 100,000.In some embodiments, the polyethylene oxide is of formulaR-Ph-O(OCH₂CH₂)_(m)OH where R is an alkyl group of from 5 to 30 carbonatoms, Ph is a phenyl group, and m is an integer having value between 5to 50. In some embodiments, the polyethylene oxide is ethoxylatednonylphenyl comprising in a range of 20 to 30 moles of ethylene oxide.In some embodiments, the polyalcohol is a C10-C18 polyalcohol.

In some embodiments of the foregoing aspects and embodiments, thestabilizer is a calcium binding agent or a carbonate binding agent. Insome embodiments, the stabilizer is incorporated in crystal lattice ofthe carbonate. In some embodiments, the stabilizer is present on thesurface of the carbonate. In some embodiments, the stabilizer stabilizesthe composition for up to 5 years. In some embodiments, the ratio ofcalcium to carbonate in the metastable carbonate is between 1:1 to1.5:1. In some embodiments, the stabilizer is an alkali metal sulfateand the sulfate in the composition is at least 0.1 wt % or between 0.1-5wt %. In some embodiments, more than 90% or between 90-99% of thesulfate in the composition is from the stabilizer. In some embodiments,the composition has a compressive strength in a range of 14-40 MPa or20-40 MPa. In some embodiments, the composition has a carbon isotopicfractionation value (δ¹³C) of less than −12‰ or between −12‰ to −25‰. Insome embodiments, the composition comprises vaterite in a range of 1%w/w to 99% w/w. In some embodiments, the composition comprises ACC in arange of 1% w/w to 99% w/w. In some embodiments, the composition is aparticulate composition with an average particle size of 0.1-100microns.

In some embodiments of the foregoing aspects and embodiments, thecomposition includes nitrogen oxide, sulfur oxide, mercury, metal,derivative of any of nitrogen oxide, sulfur oxide, mercury, and/ormetal, or combination thereof. In some embodiments, the compositionincludes Portland cement clinker, aggregate, other supplementarycementitious material (SCM), or combination thereof. In someembodiments, the other supplementary cementitious material includesslag, fly ash, etc.

In one aspect, there is provided a formed building material, comprising:the composition provided herein or the set and hardened form thereof.

In one aspect, there is provided an aggregate, comprising: thecomposition provided herein or the set and hardened form thereof.

In one aspect, there is provided a package, comprising: the compositionprovided herein and a packaging material adapted to contain thecomposition.

In one aspect, there is provided a method for making a compositionprovided herein, comprising (a) contacting CO₂ from a CO₂ source with aproton removing agent to form a solution; and (b) contacting thesolution with an alkaline earth-metal containing water under one or moreconditions to make the composition. In some embodiments, the methodfurther includes contacting the stabilizer with the solution before step(b). In some embodiments, the method further includes contacting thestabilizer with the alkaline earth-metal containing water before step(b). In some embodiments, the method further includes contacting thestabilizer with the solution simultaneously at step (b). In someembodiments, the method further includes contacting the stabilizer withthe solution after step (b). In one aspect, there is provided a methodfor making a composition provided herein, comprising (a) contacting CO₂from a CO₂ source with a proton removing agent to form a solution; and(b) contacting the solution with water comprising alkaline earth-metaland stabilizer under one or more conditions to make a compositioncomprising vaterite and stabilizer. In some embodiments, the stabilizeris added to the water comprising alkaline earth-metal before step (b).In some embodiments, the one or more conditions are selected from thegroup consisting of mixing, stirring, temperature, pH, precipitation,residence time of the precipitate, dewatering of precipitate, washingprecipitate with water, ion ratio, concentration of additives, drying,milling, grinding, storing, aging, and curing. In some embodiments, themethod further comprises activating the composition by nucleiactivation, thermal activation, mechanical activation, chemicalactivation, or combination thereof. In some embodiments, the activationcomprises adding one or more of aragonite seed, inorganic additive ororganic additive. Some examples of inorganic additive or organicadditive in the compositions provided herein, include, but not limitedto, sodium decyl sulfate, lauric acid, sodium salt of lauric acid, urea,citric acid, sodium salt of citric acid, phthalic acid, sodium salt ofphthalic acid, taurine, creatine, dextrose, poly(n-vinyl-1-pyrrolidone),aspartic acid, sodium salt of aspartic acid, magnesium chloride, aceticacid, sodium salt of acetic acid, glutamic acid, sodium salt of glutamicacid, strontium chloride, gypsum, lithium chloride, sodium chloride,glycine, sodium citrate dehydrate, sodium bicarbonate, magnesiumsulfate, magnesium acetate, sodium polystyrene, sodium dodecylsulfonate,poly-vinyl alcohol, or combination thereof. In some embodiments, themethod further comprises combining the composition with water andfacilitating vaterite transformation to aragonite when the compostionsets and hardens to form cement. In some embodiments, the facilitatingthe aragonite formation results in one or more of better linkage orbonding, higher tensile strength, or higher impact fracture toughness,after cementation of the composition. In some embodiments, the methodfurther comprises pouring the composition in a mold after combining withwater to form a formed building material. In some embodiments of themethods described herein, the activation of vaterite comprises ballmilling of the composition. In another aspect, there is provided productformed by the methods of the invention.

In one aspect, there is provided a system for making a compositionprovided herein, comprising (a) an input for an alkaline earth-metalcontaining water; (b) an input for a CO₂ source; and (c) a reactorconnected to the inputs of step (a) and step (b) that is configured tomake the composition provided herein. In one aspect, there is providedsystem for making a composition, comprising (a) an input for an alkalineearth-metal containing water; (b) an input for a CO₂ source; (c) aninput for a stabilizer source; and (d) a reactor connected to the inputsof (a), (b), and (c) that is configured to make the compositioncomprising vaterite and the stabilizer.

In one aspect, there is provided a method for making a cement productfrom the composition provided herein, comprising (a) combining thecomposition provided herein with an aqueous medium under one or moresuitable conditions; and (b) allowing the composition to set and hardeninto a cement product. In some embodiments, the one or more suitableconditions include, but not limited to, temperature, pH, pressure, timeperiod for setting, a ratio of the aqueous medium to the composition,and combination thereof. In some embodiments, the method furtherincludes combining the composition before step (a) with a Portlandcement clinker, aggregate, a supplementary cementitious material, or acombination thereof, before combining with the aqueous medium. In someembodiments, the cement product is a formed building material.

In one aspect, there is provided a system for making a cement productfrom the composition provided herein, comprising (a) an input for thecomposition provided herein; (b) an input for an aqueous medium; and (c)a reactor connected to the inputs of step (a) and step (b) configured tomix the composition provided herein with the aqueous medium under one ormore suitable conditions to make a cement product.

In one aspect, there is provided a method for making a formed buildingmaterial from the composition provided herein, comprising combining thecomposition provided herein with an aqueous medium under one or moresuitable conditions; and allowing the composition to set and harden intothe formed building material.

INCORPORATION BY REFERENCE

All publications, patents, and patent applications mentioned in thisspecification are herein incorporated by reference to the same extent asif each individual publication, patent, or patent application wasspecifically and individually indicated to be incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel features of the invention are set forth with particularity inthe appended claims. A better understanding of the features andadvantages of the present invention may be obtained by reference to thefollowing detailed description that sets forth illustrative embodiments,in which the principles of the invention are utilized, and theaccompanying drawings of which:

FIG. 1 illustrates a Gibbs free energy diagram of the transition fromvaterite to aragonite and aragonite to calcite.

FIG. 2 illustrates a flow diagram of a precipitation process accordingto some embodiments provided herein.

FIG. 3 illustrates a schematic of a system according to some embodimentsprovided herein.

FIG. 4 illustrates a schematic of a system according to some embodimentsprovided herein.

FIG. 5 illustrates data obtained in an experiment described in Example1.

FIG. 6 illustrates data obtained in an experiment described in Example1.

FIG. 7 illustrates data obtained in an experiment described in Example1.

FIG. 8 illustrates data obtained in an experiment described in Example1.

FIG. 9 illustrates data obtained in an experiment described in Example2.

FIG. 10 illustrates data obtained in an experiment described in Example3.

FIG. 11 illustrates data obtained in an experiment described in Example4.

FIG. 12 illustrates data obtained in an experiment described in Example5.

FIG. 13 illustrates data obtained in an experiment described in Example5.

FIG. 14 illustrates data obtained in an experiment described in Example6.

FIG. 15 illustrates data obtained in an experiment described in Example6.

FIG. 16 illustrates data obtained in an experiment described in Example9.

FIG. 17A and FIG. 17B illustrates data obtained in an experimentdescribed in Example 9.

DETAILED DESCRIPTION

Provided herein are compositions, methods, and systems includingcarbonate materials and stabilizers; methods and systems for making andusing the compositions; and the materials formed from such compositions,such as aggregates and formed or pre-formed building materials.

Provided herein are compositions containing metastable carbonate andstabilizer. In some embodiments, the compositions are cementitiouscompositions. The cementitious compositions include hydraulic cement,supplementary cementitious material, or self-cementing compositions thatinclude polymorph forms of calcium carbonate, such as, but not limitedto, metastable form such as vaterite (CaCO₃) alone or vaterite incombination with amorphous calcium carbonate (CaCO₃.nH₂O), aragonite(CaCO₃), calcite (CaCO₃), ikaite (CaCO₃.6H₂O), a precursor phase ofvaterite, a precursor phase of aragonite, an intermediary phase that isless stable than calcite, polymorphic forms in between these polymorphs,or combination thereof. The carbonate in the cementitious compositionsprovided herein includes one or more of metastable polymorphic forms,such as, but not limited to, vaterite, amorphous calcium carbonate, aprecursor phase of vaterite, a precursor phase of aragonite, anintermediary phase that is less stable than calcite, polymorphic formsin between these polymorphs, or combination thereof.

It was unexpectedly and surprisingly found that the use of stabilizersduring the preparation of the carbonate containing cementitiouscompositions results in more stable metastable carbonate containingcompositions or that the stability of the composition can be optimizedby optimizing the amount of the stabilizer. The metastable carbonatecontaining compositions provided herein are stable compositions in a drypowdered or wet form. The metastable forms in the compositions of theinvention convert to the stable forms, such as aragonite and/or calcite,for cementation when contacted with fresh water.

The products obtained from the compositions provided herein (eitheralone or in combination with OPC) have high compressive strengthresulting in products with high durability and less maintenance costs.The stability of the metastable carbonate in the compositions providedherein may be optimized by optimizing the amount of stabilizer or byoptimizing the step at which the stabilizer is added during thepreparation of the composition. The optimization of the stability of thecomposition may facilitate efficient control of the cementation process.

Applicants have also unexpectedly and surprisingly found that theactivation of vaterite, as described herein, facilitates aragoniticpathway and not calcite pathway during dissolution-reprecipitationprocess. In one aspect of the invention, the vaterite containingcomposition is activated in such a way that after thedissolution-reprecipitation process, aragonite formation is enhanced andcalcite formation is suppressed. The activation of the vateritecontaining composition may result in control over the aragoniteformation and crystal growth. The activation of the vaterite containingcomposition may be achieved by various processes, as described herein.

Before the present invention is described in greater detail, it is to beunderstood that this invention is not limited to particular embodimentsdescribed, as such may, of course, vary. It is also to be understoodthat the terminology used herein is for the purpose of describingparticular embodiments only, and is not intended to be limiting, sincethe scope of the present invention will be limited only by the appendedclaims.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit unlessthe context clearly dictates otherwise, between the upper and lowerlimit of that range and any other stated or intervening value in thatstated range, is encompassed within the invention. The upper and lowerlimits of these smaller ranges may independently be included in thesmaller ranges and are also encompassed within the invention, subject toany specifically excluded limit in the stated range. Where the statedrange includes one or both of the limits, ranges excluding either orboth of those included limits are also included in the invention.

Certain ranges are presented herein with numerical values being precededby the term “about.” The term “about” is used herein to provide literalsupport for the exact number that it precedes, as well as a number thatis near to or approximately the number that the term precedes. Indetermining whether a number is near to or approximately a specificallyrecited number, the near or approximating unrequited number may be anumber, which, in the context in which it is presented, provides thesubstantial equivalent of the specifically recited number.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of the present invention, representativeillustrative methods and materials are now described.

All publications and patents cited in this specification are hereinincorporated by reference as if each individual publication or patentwere specifically and individually indicated to be incorporated byreference and are incorporated herein by reference to disclose anddescribe the methods and/or materials in connection with which thepublications are cited. The citation of any publication is for itsdisclosure prior to the filing date and should not be construed as anadmission that the present invention is not entitled to antedate suchpublication by virtue of prior invention. Further, the dates ofpublication provided may be different from the actual publication dateswhich may need to be independently confirmed.

It is noted that, as used herein and in the appended claims, thesingular forms “a,” “an,” and “the” include plural references unless thecontext clearly dictates otherwise. It is further noted that the claimsmay be drafted to exclude any optional element. As such, this statementis intended to serve as antecedent basis for use of such exclusiveterminology as “solely,” “only” and the like in connection with therecitation of claim elements, or use of a “negative” limitation.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentinvention. Any recited method can be carried out in the order of eventsrecited or in any other order which is logically possible.

I. Compositions

In one aspect, there are provided cementitious compositions including ametastable carbonate and a stabilizer. The cementitious compositionsinclude hydraulic cement, supplementary cemetitious material (SCM), andself-cementing composition, where the hydraulic cement or the SCM or theself-cementing composition includes metastable and stable carbonateforms such as, vaterite, amorphous calcium carbonate (ACC), aragonite,calcite, ikaite, a precursor phase of vaterite, a precursor phase ofaragonite, an intermediary phase that is less stable than calcite,polymorphic forms in between these polymorphs, and combination thereof.The cementitious compositions provided herein may further include formsof magnesium carbonate, calcium bicarbonate, magnesium bicarbonate,calcium magnesium carbonate, calcium magnesium bicarbonate, orcombination thereof. The “cementitious” compositions as used herein,includes compositions that after combining with water set and hardeninto cement. In one aspect, there are provided non-cementitiouscompositions including a metastable carbonate and a stabilizer. Thenon-cementitious compositions include, but not limited to, paper,plastic, paint, etc.

As used herein, “metastable carbonate” includes metastable polymorphicforms of calcium carbonate such as vaterite, amorphous calciumcarbonate, a precursor phase of vaterite, a precursor phase ofaragonite, an intermediary phase that is less stable than calcite,polymorphic forms in between these polymorphs, or combination thereof.The metastable forms such as vaterite and precursor to vaterite andstable carbonate forms, such as, aragonite or calcite, may have varyingdegrees of solubility so that the metastable form, such as vaterite, maydissolve when hydrated in aqueous solutions and reprecipitate carbonateminerals, such as calcite and/or aragonite. The amorphous calciumcarbonate, precursor of vaterite, vaterite, and precursor of aragonitecan be utilized as a reactive metastable calcium carbonate forms forreaction purposes and stabilization reactions, such as cementing.

During precipitation of calcium carbonate, described herein, amorphouscalcium carbonate (ACC) may initially precipitate and transform into oneor more of its three more stable phases (vaterite, aragonite, orcalcite). A thermodynamic driving force may exist for the transformationfrom unstable phases to more stable phases, as described by Ostwald inhis Step Rule (Ostwald, W. Zeitschrift fur Physikalische Chemie 289(1897)). For this reason, calcium carbonate phases may transform in theorder: ACC to vaterite, aragonite, and calcite where intermediate phasesmay or may not be present. For instance, ACC can transform to vateriteand may not transform to aragonite or calcite; or ACC can transform tovaterite and then directly to calcite, skipping the aragonite form; oralternatively, ACC can transform to vaterite and then to aragonitewithout transforming to calcite. During this transformation, excesses ofenergy are released, as demonstrated in FIG. 1. This intrinsic energymay be harnessed to create a strong aggregation tendency and surfaceinteractions that may lead to agglomeration and cementing. It is to beunderstood that the values reported in FIG. 1 are well known in the artand may vary.

The transformation between calcium carbonate polymorphs may occur viasolid-state transition or may be solution mediated. In some embodiments,the transformation is solution-mediated because it may require lessenergy than thermally activated solid-state transition. Thesolution-mediated transformation may be environmentally conscious andmore applicable to a cementing application. Vaterite is metastable andthe difference in thermodynamic stability of calcium carbonatepolymorphs may be manifested as a difference in solubility, where theleast stable phases are the most soluble (Ostwald, supra.). Therefore,vaterite may dissolve readily in solution and transform favorablytowards a more stable polymorph: aragonite or calcite. The driving forcefor the formation of a particular calcium carbonate polymorph orcombination of polymorphs is the change in Gibbs free energy from asupersaturated solution to equilibrium (Spanos & Koutsoukos Journal ofCrystal Growth (1998) 191, 783-790).

In a polymorphic system like calcium carbonate, two kinetic processesmay exist simultaneously in solution: dissolution of the metastablephase and growth of the stable phase (Kralj et al. Journal of CrystalGrowth (1997) 177, 248-257). In some embodiments, the aragonite orcalcite crystals may be growing while vaterite may be undergoingdissolution in the aqueous medium. Crystallization of the polymorphs maybe a surface controlled process where heterogeneous nucleation may beresponsible for the formation of multiple solid phases. When a singlephase is present, the number of particles may decrease with time, whiletheir size increases (Spanos & Koutsoukos, supra.).

Vaterite in the metastable carbonate may be present in monodisperse oragglomerated form, and may be in spherical, ellipsoidal, plate likeshape, or hexagonal system. Vaterite typically has a hexagonal crystalstructure and forms polycrystalline spherical particles upon growth. Theprecursor form of vaterite comprises nanoclusters of vaterite and theprecursor form of aragonite comprises sub-micron to nanoclusters ofaragonite needles. Aragonite, if present in the composition, may beneedle shaped, columnar, or crystals of the rhombic system. Calcite, ifpresent, may be cubic, spindle, or crystals of hexagonal system. Anintermediary phase that is less stable than calcite may be a phase thatis between vaterite and calcite, a phase between precursor of vateriteand calcite, a phase between aragonite and calcite, and/or a phasebetween precursor of aragonite and calcite.

The stabilizer as provided herein may stabilize the metastable carbonateforms such that the conversion of ACC to vaterite or the conversion ofvaterite to aragonite is slowed down and the stability of the metastableform increases. In some embodiments, the stabilizer may affect the Gibbsfree energy of transformation of one form to the other. As used herein,“stabilizer” includes any reagent that stabilizes the metastable formsof carbonate in the composition. In some embodiments, the metastableform that is stabilized by the stabilizer is vaterite. In someembodiments, the stabilizer stabilizes the metastable forms of thecarbonate in the composition from hours to days to few weeks to manyyears. In some embodiments, the stabilizer stabilizes the metastableforms of the carbonate in the composition for upto 20 years; or for upto10 years; or for upto 5 years; or for upto 1 year; or from few hours to2 weeks; or from 2 weeks to 20 years; or from 2 weeks to 10 years; orfrom 2 weeks to 5 years; or from 2 weeks to 1 year; or from 2 weeks tofew months such as 6 months, 8 months etc. In some embodiments, thestability of the metastable carbonate in the composition with stabilizeris more than the stability of the metastable carbonate in thecomposition without the stabilizer. In some embodiments, the stabilizerstabilizes the metastable forms of the carbonate in the composition forfew hours to few days to few weeks.

In some embodiments, the stability of the metastable carbonate forms inthe compositions provided herein may be optimized for any period of timeby optimizing the amount of the stabilizer added during the formation ofthe composition. In some embodiments, the stability of the metastablecarbonate forms in the compositions provided herein may be optimized forany period of time by optimizing the step at which the stabilizer isadded during the formation of the composition. Therefore, thecomposition may be stabilized for a period of time based on desiredreactivity for the composition. For example, in applications such aspreformed building materials where the composition may need to berapidly cemented, a less stable metastable carbonate containingcomposition may be desired. In some embodiments, in applications wherethe composition is used as hydraulic cement, a slow cementation may bedesired and a more stable metastable carbonate containing compositionmay be formed. In some embodiments, in applications where thecomposition is used as SCM, a super stable metastable carbonatecontaining composition may be desired that may not react with the cementit is mixed with to form a stable cemented product. In some embodiments,the stabilizer imparts storage stability to the composition. In someembodiments, the cementitious composition may need to be stored for alonger period of time and the amount of stabilizer may be usedaccordingly. The amount of the stabilizer used during the formation ofthe cementitious composition may be varied depending on the desiredstability of the composition.

In some embodiments, the amount of stabilizer used during the formationof the metastable carbonate is more than 0.1% w/w; more than 0.5% w/w;more than 1% w/w; or more than 10% w/w; or more than 25% w/w/; orbetween 0.1-20% w/w; or between 0.1-15% w/w; or between 0.1-10% w/w; orbetween 0.1-5% w/w; or between 0.1-2% w/w; or between 0.1-1% w/w; orbetween 0.5-20% w/w; or between 0.5-15% w/w; or between 0.5-10% w/w; orbetween 0.5-5% w/w; or between 0.5-2% w/w; or between 0.5-1% w/w; orbetween 1-20% w/w; or between 1-15% w/w; or between 1-10% w/w; orbetween 1-5% w/w; or between 1-2% w/w; or between 1.5-20% w/w; orbetween 1.5-15% w/w; or between 1.5-10% w/w; or between 1.5-5% w/w; orbetween 1.5-2% w/w; or between 2-20% w/w; or between 2-15% w/w; orbetween 2-10% w/w; or between 2-5% w/w; or between 2-3% w/w; or between5-20% w/w; or between 5-15% w/w; or between 5-10% w/w; or between 5-8%w/w; or between 8-20% w/w; or between 8-15% w/w; or between 8-10% w/w;or between 10-15% w/w; or between 10-20% w/w; or between 15-20% w/w; or0.1% w/w; or 0.5% w/w; or 1% w/w; or 1.5% w/w; or 2% w/w; or 2.5% w/w;or 3% w/w; or 5% w/w; or 10% w/w; or 15% w/w; or 20% w/w (or by weight).In some embodiments, the above recited amounts are in weight by volume(w/v). In some embodiments, the amount of stabilizer used during theformation of the metastable carbonate or the amount of stabilizerpresent in the cementitious compositions is 1 mM (millimolar) to 50 mM;or 1 mM to 40 mM; or 1 mM to 30 mM; or 1 mM to 20 mM; or 1 mM to 10 mM;or 1 mM to 5 mM; or 1 mM to 4 mM; or 1 mM to 3 mM; or 1 mM to 2 mM; or 2mM to 50 mM; or 2 mM to 40 mM; or 2 mM to 30 mM; or 2 mM to 20 mM; or 2mM to 10 mM; or 2 mM to 5 mM; or 2 mM to 4 mM; or 2 mM to 3 mM; or 3 mMto 50 mM; or 3 mM to 40 mM; or 3 mM to 30 mM; or 3 mM to 20 mM; or 3 mMto 10 mM; or 3 mM to 5 mM; or 3 mM to 4 mM; or 4 mM to 50 mM; or 4 mM to40 mM; or 4 mM to 30 mM; or 4 mM to 20 mM; or 4 mM to 10 mM; or 4 mM to5 mM; or 5 mM to 50 mM; or 5 mM to 40 mM; or 5 mM to 30 mM; or 5 mM to20 mM; or 5 mM to 10 mM; or 6 mM to 50 mM; or 6 mM to 40 mM; or 6 mM to30 mM; or 6 mM to 20 mM; or 6 mM to 10 mM; or 7 mM to 50 mM; or 7 mM to40 mM; or 7 mM to 30 mM; or 7 mM to 20 mM; or 7 mM to 10 mM; or mM; or 2mM; or 3 mM; 4 mM; or 5 mM; or 6 mM; or 7 mM; or 8 mM; or 9 mM; or 10mM. In some embodiments, the above described amount of the stabilizer isthe amount of stabilizer present in the cementitious compositionsdescribed herein.

For example, in some embodiments, the amount of stabilizer present inthe compositions is between 0.1 wt % to 2 wt %; or between 0.1 wt % to1.5 wt %; or between 0.1 wt % to 1 wt %; or between 0.1 wt % to 0.5 wt%; or between 0.1 wt % to 0.2 wt %; or between 0.5 wt % to 2 wt %; orbetween 0.5 wt % to 1.5 wt %; or between 0.5 wt % to 1 wt %; or between1 wt % to 2 wt %; or between 1 wt % to 1.5 wt %; or between 1.5 wt % to2 wt %.

In some embodiments where sulfate such as sulfate in sea water, analkali metal sulfate, an alkaline earth metal sulfate, lignosulfate, orcombination thereof, is used as the stabilizer, some or all of sulfatein the metastable carbonate containing composition is from the sulfateadded during precipitation. In some embodiments, the sulfate present inthe metastable carbonate compositions of the invention is not from theflue gas or is in only ppm from the flue gas and the rest is from thesulfate stabilizer. For example, typically 400 scfm of flue gas enteringthe process of the invention may contain 1.3 ton/day of CO₂. Inaddition, the flue gas entering the process may contain 0.15 lb/day ofNO_(R), 0.004 lb/day of CO, and 0.0015 lb/day of SO_(X). So roughlyassuming identical capture of CO₂ and SO₂, for each 1.3 tons of CO₂captured there may be 0.0015 lbs of SO₂ in the composition of theinvention (a ratio of 1,911,000 CO₂ to 1 SO₂). This sulfur content inthe composition of the invention originating from the flue gas is inppm. Accordingly, in some embodiments, of the total sulfate stabilizerpresent in the compositions of the invention more than 90% is from thestabilizer added during the precipitation process or more than 90% isfrom sulfate such as, sodium sulfate added during the process; or morethan 95%, or between 80-99%, or between 80-99.9%, or between 90-99% orbetween 90-95%, is from sodium sulfate added during the process.

In some embodiments, there is provided a composition comprising themetastable carbonate and a stabilizer wherein the stabilizer is morethan 0.1 wt %. In some embodiments, the stabilizer is sulfate in seawater, an alkali metal sulfate, alkaline earth metal sulfate,lignosulfate, or combination thereof. In some embodiments, thestabilizer is an alkali metal sulfate. In some embodiments, thestabilizer is an alkali metal sulfate and the sulfate in the compositionis at least 0.1 wt %. In some embodiments, the more than 90% of thesulfate in the composition is from the stabilizer added during theprocess. In some embodiments, the metastable carbonate in suchcompositions comprises vaterite. In some embodiments, the amount ofvaterite in such composition is at least 50 wt % or between 50-100 wt %.In some embodiments, the composition is cementitious. In someembodiments, such composition has carbon isotopic fractionation value(δ¹³C) of less than −12‰ or between −12‰ to −25‰. Accordingly, there isprovided a composition comprising at least 50 wt % vaterite and astabilizer. In some embodiments, there is provided a compositioncomprising at least 50 wt % vaterite and at least 0.1 wt % ofstabilizer. In some embodiments, there is provided a compositioncomprising at least 50 wt % vaterite and a sulfate such as an alkalimetal sulfate, alkaline earth metal sulfate, lignosulfate, orcombination thereof. In some embodiments, there is provided acomposition comprising at least 50 wt % vaterite and at least 0.1 wt %of an alkali metal sulfate. In some embodiments, there is provided acomposition comprising at least 50 wt % or between 50-100 wt % vateriteand at least 0.1 wt % or between 0.1-1.5 wt % sulfate. In someembodiments, there is provided a composition comprising at least 50 wt %or between 50-100 wt % vaterite and at least 0.1 wt % or between 0.1-1.5wt % stabilizer wherein composition has carbon isotopic fractionationvalue (δ¹³C) of less than −12‰ or between −12‰ to −25‰. In someembodiments, there is provided a composition comprising at least 50 wt %or between 50-100 wt % vaterite and at least 0.1 wt % or between 0.1-1.5wt % sulfate wherein composition has carbon isotopic fractionation value(δ¹³C) of less than −12‰ or between −12‰ to −25‰. In some embodiments,there is provided a composition comprising at least 50 wt % or between50-100 wt % vaterite and at least 0.1 wt % or between 0.1-1.5 wt %stabilizer wherein composition has carbon isotopic fractionation value(δ¹³C) of less than −12‰ or between −12‰ to −25‰ and wherein thecomposition after combination with water sets and hardens with acompressive strength between 14-40 MPa. In some embodiments, there isprovided a composition comprising at least 50 wt % or between 50-100 wt% vaterite and at least 0.1 wt % or between 0.1-1.5 wt % sulfate whereincomposition has carbon isotopic fractionation value (δ¹³C) of less than−12‰ or between −12‰ to −25‰ and wherein the composition aftercombination with water sets and hardens with a compressive strengthbetween 14-40 MPa. In some embodiments of the above describedcompositions, the composition is a non-naturally occurring or syntheticcementitious composition selected from hydraulic cement, SCM,self-cement, or combination thereof. In some embodiments of the abovedescribed compositions, the sulfate is an alkali metal sulfate, alkalineearth metal sulfate, lignosulfate, or combination thereof. In someembodiments of the above described compositions, the vatreite is anactivated vaterite. In some embodiments of the above describedcompositions, the ratio of the calcium to carbonate (Ca:CO₃) in themetastable carbonate or vaterite is between 1:1 to 1.5:1.

In some embodiments, ratio of the calcium to carbonate (Ca:CO₃) in themetastable carbonate composition affects the partition coefficient ofthe stabilizer in the cementitious composition from the solution to thesolid. In some embodiments, the ratio of the calcium to carbonate in themetastable carbonate composition in combination with the amount ofstabilizer (e.g. as described above) in the composition, may affect thestability of the metastable carbonate composition. In some embodiments,the ratio of the calcium to carbonate in the metastable carbonatecomposition in combination with the amount of stabilizer in thecomposition (e.g. as described above), may be used to optimize thestability of the metastable carbonate composition. In some embodiments,the ratio of the calcium to the carbonate (Ca:CO₃) in the metastablecarbonate composition is in a range of 0.5:1-5:1; or 0.5:1-4:1; or0.5:1-3:1; or 0.5:1-2:1; or 0.5:1-1.9:1; or 0.5:1-1.8:1; or 0.5:1-1.7:1;or 0.5:1-1.6:1; or 0.5:1-1.5:1; or 0.5:1-1.4:1; or 0.5:1-1.3:1; or0.5:1-1.2:1; or 0.5:1-1.1:1; or 0.5:1-1:1; 1:1-5:1; or 1:1-4:1; or1:1-3:1; or 1:1-2:1; or 1:1-1.9:1; or 1:1-1.8:1; or 1:1-1.7:1; or1:1-1.6:1; or 1:1-1.5:1; or 1:1-1.4:1; or 1:1-1.3:1; or 1:1-1.2:1; or1:1-1.1:1; 2:1-5:1; or 2:1-4:1; or 2:1-3:1; 3:1-5:1; or 3:1-4:1;4:1-5:1. In some embodiments, the ratio is a molar ratio. In someembodiments, the ratio is weight ratio. In some embodiments, a higheramount of stabilizer and a higher calcium:carbonate ratio results inmore stable metastable carbonate.

In some embodiments, the ratio of the calcium:carbonate in themetastable carbonate and/or the amount of stabilizer in the cementitiouscomposition provides stability to metastable phases of the metastablecarbonate during the formation, dewatering, rinsing, and/or dryingprocess to obtain the composition. In some embodiments, these factors donot inhibit phase transformation during cemenation of vateritecomposition, such as formation of calcite and/or aragonite.

In some embodiments, the stabilizer provided herein is an organiccompound or an inorganic compound. In some embodiments, the stabilizerincludes, but not limited to, acid, ester, phosphate, sulfate,polyethylene oxide, polyalcohol, and combination thereof. Examples ofacid include, but not limited to, C₁-C₂₀ acid, sulfonic acid, or aphosphonic acid. Examples of C₁-C₂₀ acid include, but not limited to,citric acid, malic acid, adipic acid, tannic acid, lactic acid, ascorbicacid, acetic acid, fumaric acid, and mixtures thereof. Examples ofsulfonic acid include, but not limited to, copolymer of2-acrylamido-2-methyl propanesulfonic acid with acrylic acid. Examplesof phosphonic acid include, but not limited to, N-nitrilo tris(methylenephosphonic acid), 1,2-ethanediyl bis(nitrilo di(methylene phosphonicacid)); 1,6-hexanediyl bis(nitrilodi(methylene phosphonic acid)), aminotris(methylene phosphonic acid), polymethoxy polyphosphonic acid,ethylenediamine tetra(methylene phosphonic acid) (EDTMP), andcombination thereof. In some embodiments, the acids described herein,may further include an amino and/or hydroxyl group. Examples of estersinclude, but not limited to, an ester of a C₁-C₂₀ acid, a phosphonicacid, or a sulfonic acid. Such acids have been described above. In someembodiments, the stabilizer is a sulfate. The “sulfate” as used hereinincludes any molecule that provides sulfate ions in the solution.Examples of sulfate include, but not limited to, sea water, an alkalimetal sulfate, alkaline earth metal sulfate, lignosulfate, orcombination thereof. Such sulfates include, but not limited to, sodiumsulfate, potassium sulfate, calcium sulfate, magnesium sulfate, bariumsulfate, etc. In some embodiments, the sulfate is sodium sulfate. Insome embodiments, the polyethylene oxide is the polymer that has amolecular weight of between 1,000 and 100,000. Other examples ofpolyethylene oxide include, but not limited to, the polyethylene oxideof formula R-Ph-O(OCH₂CH₂)_(m)OH where R is an alkyl group of from 5 to30 carbon atoms, Ph is a phenyl group, and m is an integer having valuebetween 5 to 50. In some embodiments, the polyethylene oxide isethoxylated nonylphenyl including in a range of 20 to 30 moles ofethylene oxide. Examples of polyalcohol include, but not limited to,C10-C18 polyalcohol.

Without being limited by any theory, it is contemplated that the use ofstabilizer may result in control of one or more of the properties of themetastable carbonate including, but not limited to, polymorph,morphology, particle size, agglomeration, coagulation, aggregation,sedimentation, crystallography, inhibiting growth along a certain faceof a crystal, allowing growth along a certain face of a crystal, reducethe surface charge, increase the surface charge, or combination thereof.For example, the stabilizer may selectively target one morphology orpolymorph (based on difference in surface charge), inhibit its growthand promote the formation of another polymorph that is generally notfavorable kinetically. In some embodiments, the stabilizer may reducethe surface charge of the precipitated carbonate solids therebyincreasing the agglomeration. In some embodiments, the stabilizer maybind to the precipitated surfaces; may be a calcium binding agent orcarbonate binding agent; is incorporated in crystal lattice of thecarbonate; is absorbed on the surface of the carbonate; is bound to thecarbonate as a ligand; is present as a particle in the carbonatecomposition; is encapsulated in the carbonate; or any combinationthereof.

In one aspect, there are provided compositions including an activatedvaterite. As used herein, “activated vaterite” or its grammaticalequivalent includes vaterite that leads to aragonite formation duringand/or after dissolution-reprecipitation process. One example of thedissolution-reprecipitation process includes cementation. Thecementation process includes combining the composition with water whenit sets and hardens. Applicants unexpectedly and surprisingly found thatin some embodiments, the compositions of the invention further benefitby the activation of the metastable carbonate. Various examples of theactivation of vaterite, such as, but not limited to, nuclei activation,thermal activation, mechanical activation, chemical activation, orcombination thereof, are described herein. In some embodiments, thecomposition of the invention containing metastable carbonate isactivated such that an activated metastable carbonate is formed. Thevaterite containing compositions are activated in such a way that thecomposition results in the conversion of vaterite to aragonite duringdissolution-reprecipitation process. In some embodiments, the activationof the vaterite facilitates the conversion of the vaterite to aragonitewhile inhibiting the further conversion to calcite. In some embodiments,the vaterite is activated through various processes such that aragoniteformation and its morphology and/or crystal growth can be controlledupon reaction of vaterite containing composition with water. Thearagonite formed results in higher compressive strength and fracturetolerance to the structure built from the composition. In someembodiments, vaterite may be activated by mechanical means, as describedherein. For example, the vaterite containing compositions may beactivated by creating surface defects on the vaterite composition suchthat aragonite formation is accelerated. In some embodiments, theactivated vaterite is a ball-milled vaterite or is a vaterite withsurface defects such that aragonite formation pathway is facilitated.The vaterite containing compositions may also be activated by providingchemical or nuclei activation to the vaterite composition. Such chemicalor nuclei activation may be provided by one or more of aragonite seeds,inorganic additive, or organic additive.

In one aspect, there are provided compositions including vaterite, astabilizer, and one or more of aragonite seed, inorganic additive ororganic additive. In one aspect, there are provided compositionsincluding an activated vaterite, a stabilizer, and one or more ofaragonite seed, inorganic additive or organic additive. The presence ofaragonite seeds, inorganic addive, organic additive, or combinationthereof, in the composition, may also activate vaterite to facilitatearagonite pathway during dissolution-reprecipitation process. Theamorphous calcium carbonate, precursor of vaterite, and/or vaterite, canbe utilized as a reactive metastable calcium carbonate forms forreaction purposes and stabilization reactions, such as cementing.

In some embodiments, there are provided compositions containingvaterite, a stabilizer, and one or more of aragonite seed, inorganicadditive or organic additive where the vaterite is a ball-milledvaterite. In some embodiments, the vaterite is activated by generatingsurface defects, such as, ball-milling. Ball-milling is a process inwhich the vaterite containing material is grinded using a grinder intopowder. The ball-milling process can affect the size, density, hardness,and/or reactivity of the material.

The aragonite seed present in the compositions provided herein may beobtained from natural or synthetic sources. The natural sources include,but not limited to, reef sand, limestone, hard skeletal material ofcertain fresh-water and marine invertebrate organisms, includingpelecypods, gastropods, mollusk shell, and calcareous endoskeleton ofwarm- and cold-water corals, pearls, rocks, sediments, ore minerals(e.g., serpentine), and the like. The synthetic sources include, but notlimited to, precipitated aragonite, such as formed from sodium carbonateand calcium chloride; or aragonite formed by the transformation ofvaterite to aragonite, such as transformed vaterite described herein.

In some embodiments, the inorganic additive or organic additive in thecompositions provided herein can be any additive that activatesvaterite. Some examples of inorganic additive or organic additive in thecompositions provided herein, include, but not limited to, sodium decylsulfate, lauric acid, sodium salt of lauric acid, urea, citric acid,sodium salt of citric acid, phthalic acid, sodium salt of phthalic acid,taurine, creatine, dextrose, poly(n-vinyl-1-pyrrolidone), aspartic acid,sodium salt of aspartic acid, magnesium chloride, acetic acid, sodiumsalt of acetic acid, glutamic acid, sodium salt of glutamic acid,strontium chloride, gypsum, lithium chloride, sodium chloride, glycine,sodium citrate dehydrate, sodium bicarbonate, magnesium sulfate,magnesium acetate, sodium polystyrene, sodium dodecylsulfonate,poly-vinyl alcohol, or combination thereof. In some embodiments,inorganic additive or organic additive in the compositions providedherein, include, but not limited to, taurine, creatine,poly(n-vinyl-1-pyrrolidone), lauric acid, sodium salt of lauric acid,urea, magnesium chloride, acetic acid, sodium salt of acetic acid,strontium chloride, magnesium sulfate, magnesium acetate, or combinationthereof. In some embodiments, inorganic additive or organic additive inthe compositions provided herein, include, but not limited to, magnesiumchloride, magnesium sulfate, magnesium acetate, or combination thereof.

In some embodiments, the amount of aragonite seed, inorganic additive ororganic additive added to the composition is less than 0.01% w/w; orless than 0.1% w/w; or between 0.001-20% w/w; or between 0.001-15% w/w;or between 0.001-10% w/w; or between 0.001-5% w/w; or between 0.001-2%w/w; or between 0.001-1% w/w; or between 0.01-20% w/w; or between0.01-15% w/w; or between 0.01-10% w/w; or between 0.01-5% w/w; orbetween 0.01-2% w/w; or between 0.01-1% w/w; or between 0.1-20% w/w; orbetween 0.1-15% w/w; or between 0.1-10% w/w; or between 0.1-5% w/w; orbetween 0.1-2% w/w; or between 0.1-1% w/w; or 0.001% w/w; or 0.01% w/w;or 0.1% w/w; or 0.5% w/w; or 1% w/w; or 1.5% w/w; or 2% w/w; or 2.5%w/w; or 3% w/w; or 5% w/w; or 10% w/w; or 15% w/w; or 20% w/w (or byweight). In some embodiments, the above recited amounts are in weight byvolume (w/v). It is to be understood, that the amount of aragonite seedthat may be needed to seed the vaterite composition may be a smallamount including one or few crystals of aragonite.

Without being limited by any theory, it is contemplated that theactivation of vaterite by ball-milling or by addition of aragonite seed,inorganic additive or organic additive or combination thereof may resultin control of formation of aragonite during dissolution-reprecipitationprocess of the activated vaterite including control of properties, suchas, but not limited to, polymorph, morphology, particle size,cross-linking, agglomeration, coagulation, aggregation, sedimentation,crystallography, inhibiting growth along a certain face of a crystal,allowing growth along a certain face of a crystal, or combinationthereof. For example, the aragonite seed, inorganic additive or organicadditive may selectively target the morphology of aragonite, inhibitcalcite growth and promote the formation of aragonite that may generallynot be favorable kinetically.

In some embodiments, the cementitious compositions provided herein aresynthetic compositions and are not naturally occurring. In someembodiments, the compositions provided herein are non-medical or are notfor medical procedures. In some embodiments, the composition is in apowder form. In some embodiments, the composition is in a dry powderform. In some embodiments, the composition is disordered or is not in anordered array or is in the powdered form. In still some embodiments, thecomposition is in a partially or wholly hydrated form.

The compositions provided herein show properties, such as, highcompressive strength, high durability, and less maintenance costs. Insome embodiments, the compositions upon combination with water, setting,and hardening, have a compressive strength of at least 14 MPa(megapascal) or in some embodiments, between 14-80 MPa, or 14-40 MPa, or14-35 MPa. In some embodiments, the metastable carbonate containingcompositions provided herein are formed from CO₂ source that has afossil fuel origin. Accordingly, in some embodiments, the compositionsprovided herein have a carbon isotopic fractionation value (δ¹³C) ofless than −12‰.

In some embodiments, the cementitious composition provided herein is ahydraulic cement composition. As used herein, “hydraulic cement”includes a composition which sets and hardens after combining with wateror a solution where the solvent is water, e.g., an admixture solution.After hardening, the compositions retain strength and stability evenunder water. As a result of the immediately starting reactions,stiffening can be observed which may increase with time. After reachinga certain level, this point in time may be referred to as the start ofsetting. The consecutive further consolidation may be called setting,after which the phase of hardening begins. The compressive strength ofthe material may then grow steadily, over a period which ranges from afew days in the case of “ultra-rapid-hardening” cements, to severalmonths or years in the case of other cements. Setting and hardening ofthe product produced by combination of the composition of the inventionwith an aqueous liquid may or may not result from the production ofhydrates that may be formed from the composition upon reaction withwater, where the hydrates are essentially insoluble in water. Cementsmay be employed by themselves or in combination with aggregates, bothcoarse and fine, in which case the compositions may be referred to asconcretes or mortars. Cements may also be cut and chopped to formaggregates. In some embodiments, it may be desired to produce ahydraulic cement composition with stabilized vaterite that is stabilizedto withstand the process such as dewatering, drying etc. but that suchstabilized vaterite facilitates aragonite formation after dissolutionand reprecipitation to form cement.

In some embodiments, the cementitious composition provided herein is asupplementary cementitious material (SCM). As used herein,“supplementary cementitious material” (SCM) includes SCM as is wellknown in the art. For example, when SCM of the invention is mixed withPortland cement, one or more properties of that Portland cement afterinteraction with SCM substantially remain unchanged or are enhanced ascompared to the Portland cement itself without SCM or the Portlandcement mixed with conventional SCM (such as fly ash). The propertiesinclude, but are not limited to, fineness, soundness, consistency,setting time of cement, hardening time of cement, rheological behavior,hydration reaction, specific gravity, loss of ignition, and/or hardness,such as compressive strength of the cement. For example, when 20% of SCMof the invention is added to 80% of OPC (ordinary Portland cement), theone or more properties, such as, e.g., compressive strength, of OPCeither remain unchanged, decrease by no more than 10%, or are enhanced.The properties of Portland cement may vary depending on the type ofPortland cement. The substitution of Portland cement with the SCM of theinvention may reduce the CO₂ emissions without compromising theperformance of the cement or the concrete as compared to regularPortland cement. In some embodiments, it may be desired to produce a SCMcomposition with stabilized vaterite that is stabilized to withstand theprocess such as dewatering, drying etc. and also that such stabilizedvaterite does not transform to aragonite or transforms very slowly toaragonite after mixing with ordinary cement and after dissolution andreprecipitation to form cement, i.e. such stabilized vaterite SCMcomposition acts as a filler in the cement.

In some embodiments, the vaterite in the SCM composition of theinvention may react with the Portland cement or Portland clinker. Insome embodiments, the aluminates from the clinker fraction may combinewith the carbonate of the SCM to form carboaluminates which may reducethe porosity of the concrete and increase its strength. In someembodiments, the SCM composition of the invention may act as a filler.In some embodiments, the size of the particles and/or the surface areaof the particles may affect the interaction of the SCM composition ofthe invention with the Portland cement or Portland clinker. In someembodiments, the SCM composition of the invention may provide nucleationsites for the Portland cement or the Portland clinker. In someembodiments, the SCM composition of the invention may possess acombination of the foregoing embodiments.

In some embodiments, at least 17% by wt of SCM; or at least 18% by wt ofSCM; or at least 19% by wt of SCM; or at least 20% by wt of SCM; or atleast 21% by wt of SCM; or at least 22% by wt of SCM; or at least 23% bywt of SCM; or at least 24% by wt of SCM; or at least 25% by wt of SCM;or at least 30% by wt of SCM; or at least 40% by wt of SCM; or at least50% by wt of SCM; or between 16-50% by wt of SCM; or between 16-40% bywt of SCM; or between 16-30% by wt of SCM; or between 16-25% by wt ofSCM; or between 16-22% by wt of SCM; or between 16-20% by wt of SCM; orbetween 16-18% by wt of SCM; or between 18-50% by wt of SCM; or between18-40% by wt of SCM; or between 18-30% by wt of SCM; or between 18-20%by wt of SCM; or between 20-50% by wt of SCM; or between 20-40% by wt ofSCM; or between 20-30% by wt of SCM; or between 30-50% by wt of SCM; orbetween 30-40% by wt of SCM; or between 40-50% by wt of SCM; or 16% bywt of SCM; or 17% by wt of SCM; or 18% by wt of SCM; or 19% by wt ofSCM; or 20% by wt of SCM; or 22% by wt of SCM; or 25% by wt of SCM; or35% by wt of SCM, is mixed with OPC alone or OPC in combination withother SCM conventionally known in the art, such as, but not limited to,slag, fly ash, silica fume, calcined clay, or combination thereof.

In some embodiments, the cementitious composition provided herein is aself-cementing composition. As used herein, the “self cementing”composition is a composition that sets and hardens in water afterprecipitation of the carbonate without any step of dewatering or drying.In some embodiments, the self-cementing composition is present in water.In some embodiments, the self-cementing composition that is in waterincludes less than 90% by wt solid material; or less than 80% by wtsolid material; or less than 70% by wt solid material; or less than 60%by wt solid material; or less than 50% by wt solid material; or lessthan 40% by wt solid material; or less than 30% by wt solid material; orless than 20% by wt solid material; or less than 10% by wt solidmaterial; or between 10-90% by wt solid material; or between 10-80% bywt solid material; or between 10-70% by wt solid material; or between10-50% by wt solid material; or between 10-30% by wt solid material; orbetween 40-90% by wt solid material; or between 50-90% by wt solidmaterial. The self-cementing composition need not be dewatered and driedto make the cementitious composition. Such composition can be simplydewatered, optionally washed with water to partially or completelyremove chloride, such as, sodium chloride, optionally dewatered again,and poured into molds where it sets and hardens to form a rock, pre-castor pre-formed building materials. The rock can be further processed tomake aggregates. Such absence of the step of drying saves energy,reduces the carbon foot print, and provides a cleaner environment. Suchself-cementing composition can be artificially lithified in processesthat mimic geologic processes in which physical, rather than chemical,processes are the processes by which rocks are formed, e.g., dissolutionand reprecipitation of compounds in new forms that serve to bind thecomposition together. Such self-cementing composition, in certainembodiments, contains one or more carbonate compounds, e.g., carbonatecompounds derived from a fossil fuel source.

The self-cementing composition when rinsed with water may lead to asynthetic rock in a process in which polymorphs recited herein, such as,vaterite, is converted to more stable components, such as aragonite,calcite, or combination thereof. For example, in some embodiments, thesynthetic rock is produced from the self-cementing composition in aprocess where vaterite is converted to aragonite optionally containingcalcite. In some embodiments, it may be desired to produce aself-cementing composition with stabilized vaterite sufficientlystabilized to facilitate rapid transformation to aragonite afterdissolution and reprecipitation to form cement.

In some embodiments of the aspects and embodiments provided herein, thecementitious composition or the metastable carbonate includes at least10% w/w vaterite; or at least 20% w/w vaterite; or at least 30% w/wvaterite; or at least 40% w/w vaterite; or at least 50% w/w vaterite; orat least 60% w/w vaterite; or at least 70% w/w vaterite; or at least 80%w/w vaterite; or at least 90% w/w vaterite; or at least 95% w/wvaterite; or at least 99% w/w vaterite; or from 10% w/w to 99% w/wvaterite; or from 10% w/w to 95% w/w vaterite; or from 10% w/w to 90%w/w vaterite; or from 10% w/w to 80% w/w vaterite; or from 10% w/w to70% w/w vaterite; or from 10% w/w to 60% w/w vaterite; or from 10% w/wto 50% w/w vaterite; or from 10% w/w to 40% w/w vaterite; or from 10%w/w to 30% w/w vaterite; or from 10% w/w to 20% w/w vaterite; or from20% w/w to 99% w/w vaterite; or from 20% w/w to 95% w/w vaterite; orfrom 20% w/w to 90% w/w vaterite; or from 20% w/w to 80% w/w vaterite;or from 20% w/w to 70% w/w vaterite; or from 20% w/w to 60% w/wvaterite; or from 20% w/w to 50% w/w vaterite; or from 20% w/w to 40%w/w vaterite; or from 20% w/w to 30% w/w vaterite; or from 20% w/w to25% w/w vaterite; or from 30% w/w to 99% w/w vaterite; or from 30% w/wto 95% w/w vaterite; or from 30% w/w to 90% w/w vaterite; or from 30%w/w to 80% w/w vaterite; or from 30% w/w to 70% w/w vaterite; or from30% w/w to 60% w/w vaterite; or from 30% w/w to 50% w/w vaterite; orfrom 30% w/w to 40% w/w vaterite; or from 40% w/w to 99% w/w vaterite;or from 40% w/w to 95% w/w vaterite; or from 40% w/w to 90% w/wvaterite; or from 40% w/w to 80% w/w vaterite; or from 40% w/w to 70%w/w vaterite; or from 40% w/w to 60% w/w vaterite; or from 40% w/w to50% w/w vaterite; or from 50% w/w to 99% w/w vaterite; or from 50% w/wto 95% w/w vaterite; or from 50% w/w to 90% w/w vaterite; or from 50%w/w to 80% w/w vaterite; or from 50% w/w to 70% w/w vaterite; or from50% w/w to 60% w/w vaterite; or from 60% w/w to 99% w/w vaterite; orfrom 60% w/w to 95% w/w vaterite; or from 60% w/w to 90% w/w vaterite;or from 60% w/w to 80% w/w vaterite; or from 60% w/w to 70% w/wvaterite; or from 70% w/w to 99% w/w vaterite; or from 70% w/w to 95%w/w vaterite; or from 70% w/w to 90% w/w vaterite; or from 70% w/w to80% w/w vaterite; or from 80% w/w to 99% w/w vaterite; or from 80% w/wto 95% w/w vaterite; or from 80% w/w to 90% w/w vaterite; or from 90%w/w to 99% w/w vaterite; or from 90% w/w to 95% w/w vaterite; or 10% w/wvaterite; or 20% w/w vaterite; or 30% w/w vaterite; or 40% w/w vaterite;or 50% w/w vaterite; or 60% w/w vaterite; or 70% w/w vaterite; or 75%w/w vaterite; or 80% w/w vaterite; or 85% w/w vaterite; or 90% w/wvaterite; or 95% w/w vaterite; or 99% w/w vaterite. In some embodiments,the cementitious composition or the metastable carbonate contains atleast 50% by weight vaterite or between 50-100% by weight vaterite.

In some embodiments of the aspects and embodiments provided herein, thecementitious composition or the metastable carbonate includes at least1% w/w amorphous calcium carbonate (ACC); or at least 2% w/w ACC; or atleast 5% w/w ACC; or at least 10% w/w ACC; or at least 20% w/w ACC; orat least 30% w/w ACC; or at least 40% w/w ACC; or at least 50% w/w ACC;or at least 60% w/w ACC; or at least 70% w/w ACC; or at least 80% w/wACC; or at least 90% w/w ACC; or from 1% w/w to 90% w/w ACC; or from 1%w/w to 80% w/w ACC; or from 1% w/w to 70% w/w ACC; or from 1% w/w to 60%w/w ACC; or from 1% w/w to 50% w/w ACC; or from 1% w/w to 40% w/w ACC;or from 1% w/w to 30% w/w ACC; or from 1% w/w to 20% w/w ACC; or from 1%w/w to 10% w/w ACC; or from 5% w/w to 90% w/w ACC; or from 5% w/w to 80%w/w ACC; or from 5% w/w to 70% w/w ACC; or from 5% w/w to 60% w/w ACC;or from 5% w/w to 50% w/w ACC; or from 5% w/w to 40% w/w ACC; or from 5%w/w to 30% w/w ACC; or from 5% w/w to 20% w/w ACC; or from 5% w/w to 10%w/w ACC; or from 10% w/w to 90% w/w ACC; or from 10% w/w to 80% w/w ACC;or from 10% w/w to 70% w/w ACC; or from 10% w/w to 60% w/w ACC; or from10% w/w to 50% w/w ACC; or from 10% w/w to 40% w/w ACC; or from 10% w/wto 30% w/w ACC; or from 10% w/w to 20% w/w ACC; or from 20% w/w to 90%w/w ACC; or from 20% w/w to 80% w/w ACC; or from 20% w/w to 70% w/w ACC;or from 20% w/w to 60% w/w ACC; or from 20% w/w to 50% w/w ACC; or from20% w/w to 40% w/w ACC; or from 20% w/w to 30% w/w ACC; or from 30% w/wto 90% w/w ACC; or from 30% w/w to 80% w/w ACC; or from 30% w/w to 70%w/w ACC; or from 30% w/w to 60% w/w ACC; or from 30% w/w to 50% w/w ACC;or from 30% w/w to 40% w/w ACC; or from 40% w/w to 90% w/w ACC; or from40% w/w to 80% w/w ACC; or from 40% w/w to 70% w/w ACC; or from 40% w/wto 60% w/w ACC; or from 40% w/w to 50% w/w ACC; or from 50% w/w to 90%w/w ACC; or from 50% w/w to 80% w/w ACC; or from 50% w/w to 70% w/w ACC;or from 50% w/w to 60% w/w ACC; or from 60% w/w to 90% w/w ACC; or from60% w/w to 80% w/w ACC; or from 60% w/w to 70% w/w ACC; or from 60% w/wto 65% w/w ACC; or from 70% w/w to 90% w/w ACC; or from 70% w/w to 80%w/w ACC; or from 70% w/w to 75% w/w ACC; or from 80% w/w to 90% w/w ACC;or from 80% w/w to 85% w/w ACC; or from 85% w/w to 90% w/w ACC; or 1%w/w ACC; or 2% w/w ACC; or 5% w/w ACC; or 10% w/w ACC; or 20% w/w ACC;or 30% w/w ACC; or 40% w/w ACC; or 50% w/w ACC; or 60% w/w ACC; or 70%w/w ACC; or 80% w/w ACC; or 90% w/w ACC.

In some embodiments of the aspects and embodiments provided herein, thecomposition includes the vaterite in a range of 10% w/w to 99% w/w andthe ACC in a range of 1% w/w to 90% w/w; or the vaterite is in a rangeof 10% w/w to 90% w/w and the ACC is in a range of 10% w/w to 90% w/w;or the vaterite is in a range of 10% w/w to 80% w/w and the ACC is in arange of 20% w/w to 90% w/w; or the vaterite is in a range of 10% w/w to70% w/w and the ACC is in a range of 30% w/w to 90% w/w; or the vateriteis in a range of 10% w/w to 60% w/w and the ACC is in a range of 40% w/wto 90% w/w; or the vaterite is in a range of 10% w/w to 50% w/w and theACC is in a range of 50% w/w to 90% w/w; or the vaterite is in a rangeof 10% w/w to 40% w/w and the ACC is in a range of 60% w/w to 90% w/w;or the vaterite is in a range of 10% w/w to 30% w/w and the ACC is in arange of 70% w/w to 90% w/w; or the vaterite is in a range of 10% w/w to20% w/w and the ACC is in a range of 80% w/w to 90% w/w. It is to beunderstood that the percentage of each of the components in thecomposition will be in such a way that the total percentage of thecomponents in the composition may not exceed a total of 100% by wt.

In some embodiments of the aspects and embodiments provided herein, thecomposition after setting, and hardening has a compressive strength ofat least 14 MPa; or at least 16 MPa; or at least 18 MPa; or at least 20MPa; or at least 25 MPa; or at least 30 MPa; or at least 35 MPa; or atleast 40 MPa; or at least 45 MPa; or at least 50 MPa; or at least 55MPa; or at least 60 MPa; or at least 65 MPa; or at least 70 MPa; or atleast 75 MPa; or at least 80 MPa; or at least 85 MPa; or at least 90MPa; or at least 95 MPa; or at least 100 MPa; or from 14-100 MPa; orfrom 14-80 MPa; or from 14-75 MPa; or from 14-70 MPa; or from 14-65 MPa;or from 14-60 MPa; or from 14-55 MPa; or from 14-50 MPa; or from 14-45MPa; or from 14-40 MPa; or from 14-35 MPa; or from 14-30 MPa; or from14-25 MPa; or from 14-20 MPa; or from 14-18 MPa; or from 14-16 MPa; orfrom 17-35 MPa; or from 17-30 MPa; or from 17-25 MPa; or from 17-20 MPa;or from 17-18 MPa; or from 20-100 MPa; or from 20-90 MPa; or from 20-80MPa; or from 20-75 MPa; or from 20-70 MPa; or from 20-65 MPa; or from20-60 MPa; or from 20-55 MPa; or from 20-50 MPa; or from 20-45 MPa; orfrom 20-40 MPa; or from 20-35 MPa; or from 20-30 MPa; or from 20-25 MPa;or from 30-100 MPa; or from 30-90 MPa; or from 30-80 MPa; or from 30-75MPa; or from 30-70 MPa; or from 30-65 MPa; or from 30-60 MPa; or from30-55 MPa; or from 30-50 MPa; or from 30-45 MPa; or from 30-40 MPa; orfrom 30-35 MPa; or from 40-100 MPa; or from 40-90 MPa; or from 40-80MPa; or from 40-75 MPa; or from 40-70 MPa; or from 40-65 MPa; or from40-60 MPa; or from 40-55 MPa; or from 40-50 MPa; or from 40-45 MPa; orfrom 50-100 MPa; or from 50-90 MPa; or from 50-80 MPa; or from 50-75MPa; or from 50-70 MPa; or from 50-65 MPa; or from 50-60 MPa; or from50-55 MPa; or from 60-100 MPa; or from 60-90 MPa; or from 60-80 MPa; orfrom 60-75 MPa; or from 60-70 MPa; or from 60-65 MPa; or from 70-100MPa; or from 70-90 MPa; or from 70-80 MPa; or from 70-75 MPa; or from80-100 MPa; or from 80-90 MPa; or from 80-85 MPa; or from 90-100 MPa; orfrom 90-95 MPa; or 14 MPa; or 16 MPa; or 18 MPa; or 20 MPa; or 25 MPa;or 30 MPa; or 35 MPa; or 40 MPa; or 45 MPa. For example, in someembodiments of the aspects and embodiments provided herein, thecomposition after setting, and hardening has a compressive strength of14 MPa to 40 MPa; or 17 MPa to 40 MPa; or 20 MPa to 40 MPa; or 30 MPa to40 MPa; or 35 MPa to 40 MPa. In some embodiments, the compressivestrengths described herein are the compressive strengths after 1 day, or3 days, or 7 days, or 28 days, or 56 days, or longer.

In some embodiments, the carbonate containing compositions providedherein are formed using a gaseous stream of CO₂. The calcium carbonatein the compositions of the invention may contain carbon dioxide from anynumber of sources including, but not limited to, an industrial wastestream including flue gas from combustion; a flue gas from a chemicalprocessing plant; a flue gas from a plant that produces CO₂ as abyproduct; or combination thereof. In some embodiments, the carbondioxide sequestered into the calcium carbonate in the compositions ofthe invention, originates from the burning of fossil fuel, and thus some(e.g., at least 10, 50, 60, 70, 80, 90, 95%) or substantially all (e.g.,at least 99, 99.5, or 99.9%) of the carbon in the carbonates is offossil fuel origin, i.e., of plant origin. Typically, carbon of plantorigin has a different ratio of stable isotopes (¹³C and ¹²C) thancarbon of inorganic origin. The plants from which fossil fuels arederived preferentially utilize ¹²C over ¹³C, thus fractionating thecarbon isotopes so that the value of their ratio differs from that inthe atmosphere in general. This value, when compared to a standard value(PeeDee Belemnite, or PDB, standard), is termed the carbon isotopicfractionation (δ¹³C) value. Typically, δ¹³C values for coal are in therange −30 to −20‰; δ¹³C values for methane may be as low as −20‰ to −40‰or even −40‰ to −80‰; δ¹³C values for atmospheric CO₂ are −10‰ to −7‰;for limestone +3‰ to −3‰; and for marine bicarbonate, 0‰.

In some embodiments, the carbon in the vaterite and/or other polymorphsin the composition of the invention, has a δ¹³C of less than −12‰, −13‰, −14 ‰, −15 ‰, −20‰, or less than −25‰, or less than −30‰, or lessthan −35‰, or less than −45‰, or less than −50‰, as described in furtherdetail herein. In some embodiments, the composition of the inventionincludes a CO₂-sequestering additive including carbonates, bicarbonates,or a combination thereof, in which the carbonates, bicarbonates, or acombination thereof have a carbon isotopic fractionation (δ¹³C) valueless than −12‰.

The relative carbon isotope composition (δ¹³C) value with units of ‰(per mille) is a measure of the ratio of the concentration of two stableisotopes of carbon, namely ¹²C and ¹³C, relative to a standard offossilized belemnite (the PDB standard).

δ¹³ C‰=[(¹³ C/ ¹² C _(sample)−¹³ C/ ¹² C _(PDB standard))/(¹³ C/ ¹² C_(PDB standard))]×1000

¹²C is preferentially taken up by plants during photosynthesis and inother biological processes that use inorganic carbon because of itslower mass. The lower mass of ¹²C allows for kinetically limitedreactions to proceed more efficiently than with ¹³C. Thus, materialsthat are derived from plant material, e.g., fossil fuels, have relativecarbon isotope composition values that are less than those derived frominorganic sources. The carbon dioxide in flue gas produced from burningfossil fuels reflects the relative carbon isotope composition values ofthe organic material that was fossilized.

Material incorporating carbon from fossil fuels reflects δ¹³C valuesthat are like those of plant derived material, i.e. less than that whichincorporates carbon from atmospheric or non-plant marine sources. Theδ¹³C value of the material produced by the carbon dioxide from theburning fossil fuels can be verified by measuring the δ¹³C value of thematerial and confirming that it is not similar to the values foratmospheric carbon dioxide or marine sources of carbon. Table I belowlists relative carbon isotope composition (δ¹³C) value ranges forvarious carbon sources for comparison.

TABLE I δ¹³C Range δ¹³C Average value Carbon Source [‰] [‰] C3 Plants(most higher plants) −23 to −33 −27 C4 Plants (most tropical and  −9 to−16 −13 marsh plants) Atmosphere −6 to −7 −6 Marine Carbonate (CO₃) −2to +2 0 Marine Bicarbonate (HCO₃) −3 to +1 −1 Coal from Yallourn Seam in−27.1 to −23.2 −25.5 Australia¹ Coal from Dean Coal Bed in −24.47 to−25.14 −24.805 Kentucky, USA ² ¹HoldGate, G. R. et al, Global andPlanetary Change, 65 (2009) pp. 89-103. ² Elswick, E. R. et al., AppliedGeochemistry, 22 (2007) pp. 2065-2077.

In some embodiments, the invention provides a method of characterizingthe composition of the invention by measuring its δ¹³C value. Anysuitable method may be used for measuring the δ¹³C value, such as massspectrometry or off-axis integrated-cavity output spectroscopy (off-axisICOS). Any mass-discerning technique sensitive enough to measure theamounts of carbon, can be used to find ratios of the ¹³C to ¹²C isotopeconcentrations. The δ¹³C values can be measured by the differences inthe energies in the carbon-oxygen double bonds made by the ¹²C and ¹³Cisotopes in carbon dioxide. The δ¹³C value of a carbonate may serve as afingerprint for a CO₂ gas source, as the value can vary from source tosource. In some embodiments, the amount of carbon in the vaterite and/orpolymorphs in the compositions provided herein, may be determined anysuitable technique known in the art. Such techniques include, but arenot limited to, coulometry.

In some embodiments of the aspects and embodiments provided herein, thecomposition has a δ¹³C of less than −12‰; or less than −13‰; or lessthan −14‰; or less than −15‰; or less than −16‰; or less than −17‰; orless than −18‰; or less than −19‰; or less than −20‰; or less than −21‰;or less than −22‰; or less than −25‰; or less than −30‰; or less than−40‰; or less than −50‰; or less than −60‰; or less than −70‰; or lessthan −80‰; or less than −90‰; or less than −100‰; or from −12‰ to −80‰;or from −12‰ to −70‰; or from −12‰ to −60‰; or from −12‰ to −50‰; orfrom −12‰ to −45‰; or from −12‰ to −40‰; or from −12‰ to −35‰; or from−12‰ to −30‰; or from −12‰ to −25‰; or from −12‰ to −20‰; or from −12‰to −15‰; or from −13‰ to −80‰; or from −13‰ to −70‰; or from −13‰ to−60‰; or from −13‰ to −50‰; or from −13‰ to −45‰; or from −13‰ to −40‰;or from −13‰ to −35‰; or from −13‰ to −30‰; or from −13‰ to −25‰; orfrom −13‰ to −20‰; or from −13‰ to −15‰; from −14‰ to −80‰; or from −14‰to −70‰; or from −14‰ to −60‰; or from −14‰ to −50‰; or from −14‰ to−45‰; or from −14‰ to −40‰; or from −14‰ to −35‰; or from −14‰ to −30‰;or from −14‰ to −25‰; or from −14‰ to −20‰; or from −14‰ to −15‰; orfrom −15‰ to −80‰; or from −15‰ to −70‰; or from −15‰ to −60‰; or from−15‰ to −50‰; or from −15‰ to −45‰; or from −15‰ to −40‰; or from −15‰to −35‰; or from −15‰ to −30‰; or from −15‰ to −25‰; or from −15‰ to−20‰; or from −16‰ to −80‰; or from −16‰ to −70‰; or from −16‰ to −60‰;or from −16‰ to −50‰; or from −16‰ to −45‰; or from −16‰ to −40‰; orfrom −16‰ to −35‰; or from −16‰ to −30‰; or from −16‰ to −25‰; or from−16‰ to −20‰; or from −20‰ to −80‰; or from −20‰ to −70‰; or from −20‰to −60‰; or from −20‰ to −50‰; or from −20‰ to −40‰; or from −20‰ to−35‰; or from −20‰ to −30‰; or from −20‰ to −25‰; or from −30‰ to −80‰;or from −30‰ to −70‰; or from −30‰ to −60‰; or from −30‰ to −50‰; orfrom −30‰ to −40‰; or from −40‰ to −80‰; or from −40‰ to −70‰; or from−40‰ to −60‰; or from −40‰ to −50‰; or from −50‰ to −80‰; or from −50‰to −70‰; or from −50‰ to −60‰; or from −60‰ to −80‰; or from −60‰ to−70‰; or from −70‰ to −80‰; or −12‰; or −13‰; or −14‰; or −15‰; or −16‰;or −17‰; or −18‰; or −19‰; or −20‰; or −21‰; or −22‰; or −25‰; or −30‰;or −40‰; or −50‰; or −60‰; or −70‰; or −80‰; or −90‰; or −100‰.

In some embodiments, the vaterite and the one or more polymorphs, in thecompositions provided herein, are in a vaterite:one or more polymorphratio of greater than 1:1; or a ratio of greater than 2:1; or a ratio ofgreater than 3:1; or a ratio of greater than 4:1; or a ratio of greaterthan 5:1; or a ratio of greater than 6:1; or a ratio of greater than7:1; or a ratio of greater than 8:1; or a ratio of greater than 9:1; ora ratio of greater than 10:1; or a ratio of greater than 11:1; or aratio of greater than 12:1; or a ratio of greater than 13:1; or a ratioof greater than 14:1; or a ratio of greater than 15:1; or a ratio ofgreater than 16:1; or a ratio of greater than 17:1; or a ratio ofgreater than 18:1; or a ratio of greater than 19:1; or a ratio ofgreater than 20:1; or a ratio of 1:1 to 20:1; or a ratio of 1:1 to 18:1;or a ratio of 1:1 to 15:1; or a ratio of 1:1 to 10:1; or a ratio of 1:1to 9:1; or a ratio of 1:1 to 8:1; or a ratio of 1:1 to 7:1; or a ratioof 1:1 to 6:1; or a ratio of 1:1 to 5:1; or a ratio of 1:1 to 4:1; or aratio of 1:1 to 3:1; or a ratio of 1:1 to 2:1; or a ratio of 2:1 to20:1; or a ratio of 2:1 to 15:1; or a ratio of 2:1 to 10:1; or a ratioof 2:1 to 9:1; or a ratio of 2:1 to 8:1; or a ratio of 2:1 to 7:1; or aratio of 2:1 to 6:1; or a ratio of 2:1 to 5:1; or a ratio of 2:1 to 4:1;or a ratio of 2:1 to 3:1; or a ratio of 5:1 to 20:1; or a ratio of 5:1to 15:1; or a ratio of 5:1 to 10:1; or a ratio of 5:1 to 8:1; or a ratioof 7:1 to 20:1; or a ratio of 7:1 to 15:1; or a ratio of 7:1 to 10:1; ora ratio of 7:1 to 9:1; or a ratio of 10:1 to 20:1; or a ratio of 10:1 to15:1; or a ratio of 10:1 to 12:1; or a ratio of 15:1 to 20:1; or a ratioof 15:1 to 18:1; or a ratio of 1:1; or a ratio of 2:1; or a ratio of3:1; or a ratio of 4:1; or a ratio of 5:1; or a ratio of 6:1; or a ratioof 7:1; or a ratio of 8:1; or a ratio of 9:1; or a ratio of 10:1; or aratio of 11:1; or a ratio of 12:1; or a ratio of 13:1; or a ratio of14:1; or a ratio of 15:1; or a ratio of 16:1; or a ratio of 17:1; or aratio of 18:1; or a ratio of 19:1; or a ratio of 20:1.

In some embodiments, the vaterite and the polymorph in the compositionsprovided herein are in a vaterite:one or more polymorph ratio of lessthan 1:1; or 0.1:1; or 0.2:1; or 0.3:1; or 0.4:1; or 0.5:1; or 0.6:1; or0.7:1; or 0.8:1; or 0.9:1; or 0.1:1-10:1; or 0.2:1-10:1; or 0.3:1-10:1;or 0.4:1-10:1; or 0.5:1-10:1; or 0.6:1-10:1; or 0.7:1-10:1; or0.8:1-10:1; or 0.9:1-10:1.

In some embodiments of the aspects and embodiments provided herein, thecomposition further includes 1% w/w to 85% w/w aragonite, 1% w/w to 85%w/w calcite, 1% w/w to 85% w/w ikaite, or combination thereof.

In some embodiments, the compositions in the aspects and embodimentsprovided herein, further include at least 1% w/w ACC and at least 1% w/waragonite; at least 1% w/w ACC and at least 1% w/w calcite; at least 1%w/w ACC and at least 1% w/w ikaite; at least 1% w/w aragonite and atleast 1% w/w calcite; at least 1% w/w aragonite and at least 1% w/wikaite; at least 1% w/w calcite and at least 1% w/w ikaite; at least 1%w/w ACC, at least 1% w/w aragonite, and at least 1% w/w calcite; atleast 1% w/w ACC, at least 1% w/w aragonite, and at least 1% w/w ikaite;at least 1% w/w ACC, at least 1% w/w ikaite, and at least 1% w/wcalcite; at least 1% w/w aragonite, at least 1% w/w calcite, and atleast 1% w/w ikaite; at least 1% w/w ACC, at least 1% w/w aragonite, atleast 1% w/w calcite, and at least 1% w/w ikaite.

In some embodiments, the compositions in the aspects and embodimentsprovided herein, further include at least 1% w/w to 90% w/w ACC and atleast 1% w/w to 85% w/w aragonite; at least 1% w/w to 90% w/w ACC and atleast 1% w/w to 85% w/w calcite; at least 1% w/w to 90% w/w ACC and atleast 1% w/w to 85% w/w ikaite; at least 1% w/w to 85% w/w aragonite andat least 1% w/w to 85% w/w calcite; at least 1% w/w to 85% w/w aragoniteand at least 1% w/w to 85% w/w ikaite; at least 1% w/w to 85% w/wcalcite and at least 1% w/w to 85% w/w ikaite; at least 1% w/w to 90%w/w ACC, at least 1% w/w to 85% w/w aragonite, and at least 1% w/w to85% w/w calcite; at least 1% w/w to 90% w/w ACC, at least 1% w/w to 85%w/w aragonite, and at least 1% w/w to 85% w/w ikaite; at least 1% w/w to90% w/w ACC, at least 1% w/w to 85% w/w ikaite, and at least 1% w/w to85% w/w calcite; at least 1% w/w to 85% w/w aragonite, at least 1% w/wto 85% w/w calcite, and at least 1% w/w to 85% w/w ikaite; at least 1%w/w to 90% w/w ACC, at least 1% w/w to 85% w/w aragonite, at least 1%w/w to 85% w/w calcite, and at least 1% w/w to 85% w/w ikaite.

In some embodiments of the aspects and embodiments provided herein, thecompositions further includes at least 1% w/w aragonite; or at least 2%w/w aragonite; or at least 5% w/w aragonite; or at least 10% w/waragonite; or at least 20% w/w aragonite; or at least 30% w/w aragonite;or at least 40% w/w aragonite; or at least 50% w/w aragonite; or atleast 60% w/w aragonite; or at least 70% w/w aragonite; or at least 80%w/w aragonite; or at least 85% w/w aragonite; or from 1% w/w to 85% w/waragonite; or from 1% w/w to 80% w/w aragonite; or from 1% w/w to 70%w/w aragonite; or from 1% w/w to 60% w/w aragonite; or from 1% w/w to50% w/w aragonite; or from 1% w/w to 40% w/w aragonite; or from 1% w/wto 30% w/w aragonite; or from 1% w/w to 20% w/w aragonite; or from 1%w/w to 10% w/w aragonite; or from 5% w/w to 85% w/w aragonite; or from5% w/w to 80% w/w aragonite; or from 5% w/w to 70% w/w aragonite; orfrom 5% w/w to 60% w/w aragonite; or from 5% w/w to 50% w/w aragonite;or from 5% w/w to 40% w/w aragonite; or from 5% w/w to 30% w/waragonite; or from 5% w/w to 20% w/w aragonite; or from 5% w/w to 10%w/w aragonite; or from 10% w/w to 85% w/w aragonite; or from 10% w/w to80% w/w aragonite; or from 10% w/w to 70% w/w aragonite; or from 10% w/wto 60% w/w aragonite; or from 10% w/w to 50% w/w aragonite; or from 10%w/w to 40% w/w aragonite; or from 10% w/w to 30% w/w aragonite; or from10% w/w to 20% w/w aragonite; or from 20% w/w to 85% w/w aragonite; orfrom 20% w/w to 80% w/w aragonite; or from 20% w/w to 70% w/w aragonite;or from 20% w/w to 60% w/w aragonite; or from 20% w/w to 50% w/waragonite; or from 20% w/w to 40% w/w aragonite; or from 20% w/w to 30%w/w aragonite; or from 30% w/w to 85% w/w aragonite; or from 30% w/w to80% w/w aragonite; or from 30% w/w to 70% w/w aragonite; or from 30% w/wto 60% w/w aragonite; or from 30% w/w to 50% w/w aragonite; or from 30%w/w to 40% w/w aragonite; or from 40% w/w to 85% w/w aragonite; or from40% w/w to 80% w/w aragonite; or from 40% w/w to 70% w/w aragonite; orfrom 40% w/w to 60% w/w aragonite; or from 40% w/w to 50% w/w aragonite;or from 50% w/w to 85% w/w aragonite; or from 50% w/w to 80% w/waragonite; or from 50% w/w to 70% w/w aragonite; or from 50% w/w to 60%w/w aragonite; or from 60% w/w to 85% w/w aragonite; or from 60% w/w to80% w/w aragonite; or from 60% w/w to 70% w/w aragonite; or from 60% w/wto 65% w/w aragonite; or from 70% w/w to 85% w/w aragonite; or from 70%w/w to 80% w/w aragonite; or from 70% w/w to 75% w/w aragonite; or from80% w/w to 85% w/w aragonite; or 1% w/w aragonite; or 2% w/w aragonite;or 5% w/w aragonite; or 10% w/w aragonite; or 20% w/w aragonite; or 30%w/w aragonite; or 40% w/w aragonite; or 50% w/w aragonite; or 60% w/waragonite; or 70% w/w aragonite; or 80% w/w aragonite; or 85% w/waragonite.

In some embodiments of the aspects and embodiments provided herein, thecompositions further includes at least 1% w/w calcite; or at least 2%w/w calcite; or at least 5% w/w calcite; or at least 10% w/w calcite; orat least 20% w/w calcite; or at least 30% w/w calcite; or at least 40%w/w calcite; or at least 50% w/w calcite; or at least 60% w/w calcite;or at least 70% w/w calcite; or at least 80% w/w calcite; or at least85% w/w calcite; or from 1% w/w to 85% w/w calcite; or from 1% w/w to80% w/w calcite; or from 1% w/w to 75% w/w calcite; or from 1% w/w to70% w/w calcite; or from 1% w/w to 65% w/w calcite; or from 1% w/w to60% w/w calcite; or from 1% w/w to 55% w/w calcite; or from 1% w/w to50% w/w calcite; or from 1% w/w to 45% w/w calcite; or from 1% w/w to40% w/w calcite; or from 1% w/w to 35% w/w calcite; or from 1% w/w to30% w/w calcite; or from 1% w/w to 25% w/w calcite; or from 1% w/w to20% w/w calcite; or from 1% w/w to 15% w/w calcite; or from 1% w/w to10% w/w calcite; or from 5% w/w to 85% w/w calcite; or from 5% w/w to80% w/w calcite; or from 5% w/w to 70% w/w calcite; or from 5% w/w to60% w/w calcite; or from 5% w/w to 50% w/w calcite; or from 5% w/w to40% w/w calcite; or from 5% w/w to 30% w/w calcite; or from 5% w/w to20% w/w calcite; or from 5% w/w to 10% w/w calcite; or from 10% w/w to85% w/w calcite; or from 10% w/w to 80% w/w calcite; or from 10% w/w to70% w/w calcite; or from 10% w/w to 60% w/w calcite; or from 10% w/w to50% w/w calcite; or from 10% w/w to 40% w/w calcite; or from 10% w/w to30% w/w calcite; or from 10% w/w to 20% w/w calcite; or from 20% w/w to85% w/w calcite; or from 20% w/w to 80% w/w calcite; or from 20% w/w to70% w/w calcite; or from 20% w/w to 60% w/w calcite; or from 20% w/w to50% w/w calcite; or from 20% w/w to 40% w/w calcite; or from 20% w/w to30% w/w calcite; or from 30% w/w to 85% w/w calcite; or from 30% w/w to80% w/w calcite; or from 30% w/w to 70% w/w calcite; or from 30% w/w to60% w/w calcite; or from 30% w/w to 50% w/w calcite; or from 30% w/w to40% w/w calcite; or from 40% w/w to 85% w/w calcite; or from 40% w/w to80% w/w calcite; or from 40% w/w to 70% w/w calcite; or from 40% w/w to60% w/w calcite; or from 40% w/w to 50% w/w calcite; or from 50% w/w to85% w/w calcite; or from 50% w/w to 80% w/w calcite; or from 50% w/w to70% w/w calcite; or from 50% w/w to 60% w/w calcite; or from 60% w/w to85% w/w calcite; or from 60% w/w to 80% w/w calcite; or from 60% w/w to70% w/w calcite; or from 60% w/w to 65% w/w calcite; or from 70% w/w to85% w/w calcite; or from 70% w/w to 80% w/w calcite; or from 70% w/w to75% w/w calcite; or from 80% w/w to 85% w/w calcite; or 1% w/w calcite;or 2% w/w calcite; or 5% w/w calcite; or 10% w/w calcite; or 20% w/wcalcite; or 30% w/w calcite; or 40% w/w calcite; or 50% w/w calcite; or60% w/w calcite; or 70% w/w calcite; or 80% w/w calcite; or 85% w/wcalcite.

The compositions provided herein may include a number of differentcations, such as, but are not limited to, calcium, magnesium, sodium,potassium, sulfur, boron, silicon, strontium, and combinations thereof,where carbonate minerals include, but are not limited to: calciumcarbonate minerals, magnesium carbonate minerals and calcium magnesiumcarbonate minerals. Calcium carbonate minerals in the composition of theinvention include, but are not limited to: vaterite alone or incombination with calcite, aragonite, ikaite, amorphous calciumcarbonate, a precursor phase of vaterite, a precursor phase ofaragonite, an intermediary phase that is less stable than calcite,polymorphic forms in between these polymorphs, or combination thereof.These carbonate minerals may also be present in combination withmagnesium carbonate minerals. Magnesium carbonate minerals include, butare not limited to, magnesite (MgCO₃), barringtonite (MgCO₃.2H₂O),nesquehonite (MgCO₃.3H₂O), lanfordite (MgCO₃.5H₂O) and amorphousmagnesium calcium carbonate (MgCO₃.nH₂O). The carbonate minerals in thecomposition of the invention may also be present in combination withcalcium magnesium carbonate minerals which include, but are not limitedto, dolomite (CaMgCO₃), huntitte (CaMg(CO₃)₄) and sergeevite(Ca₂Mg₁₁(CO₃)₁₃.H₂O). Other calcium mineral that may be present in thecomposition of the invention, is portlandite (Ca(OH)₂), and amorphoushydrated analogs thereof. Other magnesium mineral that may be present inthe composition of the invention, is brucite (Mg(OH)₂), and amorphoushydrated analogs thereof.

In some embodiments of the aspects and embodiments provided herein, thecomposition further includes strontium (Sr). In some embodiments, the Sris present in the composition in an amount of 1-50,000 parts per million(ppm); or 1-10,000 ppm; or 1-5,000 ppm; or 1-1,000 ppm; or 3-50,000 ppm;or 3-10,000 ppm; or 3-9,000 ppm; or 3-8,000 ppm; or 3-7,000 ppm; or3-6,000 ppm; or 3-5,000 ppm; or 3-4,000 ppm; or 3-3,000 ppm; or 3-2,000ppm; or 3-1,000 ppm; or 3-900 ppm; or 3-800 ppm; or 3-700 ppm; or 3-600ppm; or 3-500 ppm; or 3-400 ppm; or 3-300 ppm; or 3-200 ppm; or 3-100ppm; or 3-50 ppm; or 3-10 ppm; or 10-50,000 ppm; or 10-10,000 ppm; or10-9,000 ppm; or 10-8,000 ppm; or 10-7,000 ppm; or 10-6,000 ppm; or10-5,000 ppm; or 10-4,000 ppm; or 10-3,000 ppm; or 10-2,000 ppm; or10-1,000 ppm; or 10-900 ppm; or 10-800 ppm; or 10-700 ppm; or 10-600ppm; or 10-500 ppm; or 10-400 ppm; or 10-300 ppm; or 10-200 ppm; or10-100 ppm; or 10-50 ppm; or 100-50,000 ppm; or 100-10,000 ppm; or100-9,000 ppm; or 100-8,000 ppm; or 100-7,000 ppm; or 100-6,000 ppm; or100-5,000 ppm; or 100-4,000 ppm; or 100-3,000 ppm; or 100-2,000 ppm; or100-1,000 ppm; or 100-900 ppm; or 100-800 ppm; or 100-700 ppm; or100-600 ppm; or 100-500 ppm; or 100-400 ppm; or 100-300 ppm; or 100-200ppm; or 200-50,000 ppm; or 200-10,000 ppm; or 200-1,000 ppm; or 200-500ppm; or 500-50,000 ppm; or 500-10,000 ppm; or 500-1,000 ppm; or 10 ppm;or 100 ppm; or 200 ppm; or 500 ppm; or 1000 ppm; or 5000 ppm; or 8000ppm; or 10,000 ppm.

In some embodiments, the above recited Sr is present in a crystallattice of the vaterite. In some embodiments, the above recited Sr ispresent in a crystal lattice of the aragonite. In some embodiments, theabove recited Sr is present in a crystal lattice of the calcite. In someembodiments, the above recited Sr is present in a crystal lattice of theikaite. In some embodiments, the above recited Sr is present in acrystal lattice of one or more of vaterite, aragonite, calcite, andikaite. In some embodiments, the Sr is encapsulated in the carbonatemineral.

The water employed in the invention may be fresh water, saltwater, or analkaline-earth-metal-containing water, depending on the method employingthe water. In some embodiments, the water employed in the processincludes one or more alkaline earth metals, e.g., magnesium, calcium,etc. The various types of water that may be employed in the inventionare described below. In some embodiments, the water contains calcium inamounts ranging from 50 to 20,000 ppm; or 50 to 10,000 ppm; or 50 to5,000 ppm; or 50 to 1,000 ppm; or 50 to 500 ppm; or 50 to 100 ppm; or100 to 20,000 ppm; or 100 to 10,000 ppm; or 100 to 5,000 ppm; or 100 to1,000 ppm; or 100 to 500 ppm; or 500 to 20,000 ppm; or 500 to 10,000ppm; or 500 to 5,000 ppm; or 500 to 1,000 ppm; or 1,000 to 20,000 ppm;or 1,000 to 10,000 ppm; or 1,000 to 5,000 ppm; or 5,000 to 20,000 ppm;or 5,000 to 10,000 ppm; or 10,000 to 20,000 ppm.

In some embodiments, the water contains magnesium in amounts rangingfrom 50 to 20,000 ppm; or 50 to 10,000 ppm; or 50 to 5,000 ppm; or 50 to1,000 ppm; or 50 to 500 ppm; or 50 to 100 ppm; or 100 to 20,000 ppm; or100 to 10,000 ppm; or 100 to 5,000 ppm; or 100 to 1,000 ppm; or 100 to500 ppm; or 500 to 20,000 ppm; or 500 to 10,000 ppm; or 500 to 5,000ppm; or 500 to 1,000 ppm; or 1,000 to 20,000 ppm; or 1,000 to 10,000ppm; or 1,000 to 5,000 ppm; or 5,000 to 20,000 ppm; or 5,000 to 10,000ppm; or 10,000 to 20,000 ppm.

The composition has, in certain embodiments, a calcium/magnesium ratiothat is influenced by, and therefore reflects, the water source fromwhich it has been precipitated, e.g., seawater, which contains moremagnesium than calcium, or, e.g., certain brines, which may containone-hundred-fold the calcium content as seawater; the calcium/magnesiumratio also reflects factors such as the addition of calcium and/ormagnesium-containing substances during the production process, e.g., theuse of flyash, red mud, slag, or other calcium and/ormagnesium-containing industrial wastes, or the use of calcium and/ormagnesium-containing minerals such as mafic and ultramafic minerals,such as serpentine, olivine, and the like. Because of the largevariation in raw materials as well as materials added during production,the calcium/magnesium molar ratio may vary widely in various embodimentsof the compositions and methods provided herein, and indeed in certainembodiment the ratio may be adjusted according to the intended use ofthe composition.

In some embodiments of the aspects and embodiments provided herein, thecomposition further includes magnesium (Mg). In some embodiments, Mg ispresent as magnesium carbonate. In some embodiments, a ratio of calciumto magnesium (Ca:Mg) or the ratio of vaterite:magnesium carbonate isgreater than 1:1; or a ratio of greater than 2:1; or a ratio of greaterthan 3:1; or a ratio of greater than 4:1; or a ratio of greater than5:1; or a ratio of greater than 6:1; or a ratio of greater than 7:1; ora ratio of greater than 8:1; or a ratio of greater than 9:1; or a ratioof greater than 10:1; or a ratio of greater than 15:1; or a ratio ofgreater than 20:1; or a ratio of greater than 30:1; or a ratio ofgreater than 40:1; or a ratio of greater than 50:1; or a ratio ofgreater than 60:1; or a ratio of greater than 70:1; or a ratio ofgreater than 80:1; or a ratio of greater than 90:1; or a ratio ofgreater than 100:1; or a ratio of greater than 150:1; or a ratio ofgreater than 200:1; or a ratio of greater than 250:1; or a ratio ofgreater than 300:1; or a ratio of greater than 350:1; or a ratio ofgreater than 400:1; or a ratio of greater than 450:1; or a ratio ofgreater than 500:1; or a ratio of 1:1 to 500:1; or a ratio of 1:1 to450:1; or a ratio of 1:1 to 400:1; or a ratio of 1:1 to 350:1; or aratio of 1:1 to 300:1; or a ratio of 1:1 to 250:1; or a ratio of 1:1 to200:1; or a ratio of 1:1 to 150:1; or a ratio of 1:1 to 100:1; or aratio of 1:1 to 50:1; or a ratio of 1:1 to 25:1; or a ratio of 1:1 to10:1; or a ratio of 5:1 to 500:1; or a ratio of 5:1 to 450:1; or a ratioof 5:1 to 400:1; or a ratio of 5:1 to 350:1; or a ratio of 5:1 to 300:1;or a ratio of 5:1 to 250:1; or a ratio of 5:1 to 200:1; or a ratio of5:1 to 150:1; or a ratio of 5:1 to 100:1; or a ratio of 5:1 to 50:1; ora ratio of 5:1 to 25:1; or a ratio of 5:1 to 10:1; or a ratio of 50:1 to500:1; or a ratio of 50:1 to 450:1; or a ratio of 50:1 to 400:1; or aratio of 50:1 to 350:1; or a ratio of 50:1 to 300:1; or a ratio of 50:1to 250:1; or a ratio of 50:1 to 200:1; or a ratio of 50:1 to 150:1; or aratio of 50:1 to 100:1; or a ratio of 1:1; or a ratio of 2:1; or a ratioof 3:1; or a ratio of 4:1; or a ratio of 5:1; or a ratio of 6:1; or aratio of 7:1; or a ratio of 8:1; or a ratio of 9:1; or a ratio of 10:1;or a ratio of 11:1; or a ratio of 15:1; or a ratio of 20:1; or a ratioof 30:1; or a ratio of 40:1; or a ratio of 50:1; or a ratio of 60:1; ora ratio of 70:1; or a ratio of 80:1; or a ratio of 90:1; or a ratio of100:1; or a ratio of 150:1; or a ratio of 200:1; or a ratio of 250:1; ora ratio of 300:1; or a ratio of 350:1; or a ratio of 400:1; or a ratioof 450:1; or a ratio of 500:1. In some embodiments, the ratio of calciumto magnesium (Ca:Mg) is between 2:1 to 5:1, or greater than 4:1, or 4:1.In some embodiments, the ratios herein are molar ratios or weight (suchas, grams, mg or ppm) ratios.

In some embodiments, a ratio of magnesium to calcium (Mg:Ca) or theratio of magnesium carbonate: vaterite is between 1:1 to 10:1; orbetween 2:1 to 10:1; or between 3:1 to 10:1; or between 4:1 to 10:1; orbetween 5:1 to 10:1; or between 6:1 to 10:1; or between 7:1 to 10:1; orbetween 8:1 to 10:1; or between 9:1 to 10:1.

In some embodiments, the amount of Mg present in the compositionsprovided herein is less than 2% w/w; or less than 1.5% w/w; or less than1% w/w; or less than 0.5% w/w; or less than 0.1% w/w; or between 0.1%w/w Mg to 5% w/w Mg; or between 0.1% w/w Mg to 2% w/w Mg; or between0.1% w/w Mg to 1.5% w/w Mg; or between 0.1% w/w Mg to 1% w/w Mg; orbetween 0.1% w/w Mg to 0.5% w/w Mg.

Alternatively, in some embodiments, the ratio of calcium to magnesium(Ca:Mg) is 0.1; or 0.2; or 0.3; or 0.4; or 0.5.

In some embodiments, the compositions provided herein further includesodium. In such compositions the sodium is present in an amount lessthan 100,000 ppm; or less than 80,000 ppm; or less than 50,000 ppm; orless than 20,000 ppm; or less than 15,000 ppm; or less than 10,000 ppm;or less than 5,000 ppm; or less than 1,000 ppm; or less than 500 ppm; orless than 400 ppm; or less than 300 ppm; or less than 200 ppm; or lessthan 100 ppm; or between 100 ppm to 100,000 ppm; or between 100 ppm to50,000 ppm; or between 100 ppm to 30,000 ppm; or between 100 ppm to20,000 ppm; or between 100 ppm to 15,000 ppm; or between 100 ppm to10,000 ppm; or between 100 ppm to 5,000 ppm; or between 100 ppm to 1,000ppm; or between 100 ppm to 500 ppm; or between 100 ppm to 400 ppm; orbetween 100 ppm to 300 ppm; or between 100 ppm to 200 ppm; or between500 ppm to 100,000 ppm; or between 500 ppm to 50,000 ppm; or between 500ppm to 30,000 ppm; or between 500 ppm to 20,000 ppm; or between 500 ppmto 15,000 ppm; or between 500 ppm to 10,000 ppm; or between 500 ppm to5,000 ppm; or between 500 ppm to 1,000 ppm; or between 1000 ppm to100,000 ppm; or between 1000 ppm to 50,000 ppm; or between 1000 ppm to30,000 ppm; or between 1000 ppm to 20,000 ppm; or between 1000 ppm to15,000 ppm; or between 1000 ppm to 10,000 ppm; or between 1000 ppm to5,000 ppm; or between 5000 ppm to 100,000 ppm; or between 5000 ppm to50,000 ppm; or between 10,000 ppm to 100,000 ppm; or between 10,000 ppmto 50,000 ppm; or between 50,000 ppm to 100,000 ppm; or 20,000 ppm; or15,000 ppm; or 10,000 ppm; or 5,000 ppm; or 1,000 ppm; or 500 ppm; or400 ppm; or 300 ppm; or 200 ppm; or 100 ppm.

In some embodiments, the compositions provided herein do not includecalcium phosphate. In some embodiments, the compositions include calciumphosphate. In such compositions, the calcium phosphate is in an amountof less than 20,000 ppm; or less than 15,000 ppm; or less than 10,000ppm; or less than 5,000 ppm; or less than 1,000 ppm; or less than 500ppm; or less than 400 ppm; or less than 300 ppm; or less than 200 ppm;or less than 100 ppm; or between 100 ppm to 20,000 ppm; or between 100ppm to 15,000 ppm; or between 100 ppm to 10,000 ppm; or between 100 ppmto 5,000 ppm; or between 100 ppm to 1,000 ppm; or between 100 ppm to 500ppm; or between 100 ppm to 400 ppm; or between 100 ppm to 300 ppm; orbetween 100 ppm to 200 ppm; or 20,000 ppm; or 15,000 ppm; or 10,000 ppm;or 5,000 ppm; or 1,000 ppm; or 500 ppm; or 400 ppm; or 300 ppm; or 200ppm; or 100 ppm.

In some embodiments, the composition provided herein is a particulatecomposition with an average particle size of 0.1-100 microns. Theaverage particle size may be determined using any conventional particlesize determination method, such as, but is not limited to,multi-detector laser scattering or sieving (i.e. <38 microns). Incertain embodiments, unimodel or multimodal, e.g., bimodal or other,distributions are present. Bimodal distributions allow the surface areato be minimized, thus allowing a lower liquids/solids mass ratio for thecement yet providing smaller reactive particles for early reaction. Insuch instances, the average particle size of the larger size class canbe upwards of 1000 microns (1 mm). In some embodiments, the compositionprovided herein is a particulate composition with an average particlesize of 0.1-1000 microns; or 0.1-900 microns; or 0.1-800 microns; or0.1-700 microns; or 0.1-600 microns; or 0.1-500 microns; or 0.1-400microns; or 0.1-300 microns; or 0.1-200 microns; or 0.1-100 microns; or0.1-90 microns; or 0.1-80 microns; or 0.1-70 microns; or 0.1-60 microns;or 0.1-50 microns; or 0.1-40 microns; or 0.1-30 microns; or 0.1-20microns; or 0.1-10 microns; or 0.1-5 microns; or 0.5-100 microns; or0.5-90 microns; or 0.5-80 microns; or 0.5-70 microns; or 0.5-60 microns;or 0.5-50 microns; or 0.5-40 microns; or 0.5-30 microns; or 0.5-20microns; or 0.5-10 microns; or 0.5-5 microns; or 1-100 microns; or 1-90microns; or 1-80 microns; or 1-70 microns; or 1-60 microns; or 1-50microns; or 1-40 microns; or 1-30 microns; or 1-20 microns; or 1-10microns; or 1-5 microns; or 3-100 microns; or 3-90 microns; or 3-80microns; or 3-70 microns; or 3-60 microns; or 3-50 microns; or 3-40microns; or 3-30 microns; or 3-20 microns; or 3-10 microns; or 3-8microns; or 5-100 microns; or 5-90 microns; or 5-80 microns; or 5-70microns; or 5-60 microns; or 5-50 microns; or 5-40 microns; or 5-30microns; or 5-20 microns; or 5-10 microns; or 5-8 microns; or 8-100microns; or 8-90 microns; or 8-80 microns; or 8-70 microns; or 8-60microns; or 8-50 microns; or 8-40 microns; or 8-30 microns; or 8-20microns; or 8-10 microns; or 10-100 microns; or 10-90 microns; or 10-80microns; or 10-70 microns; or 10-60 microns; or 10-50 microns; or 10-40microns; or 10-30 microns; or 10-20 microns; or 10-15 microns; or 15-100microns; or 15-90 microns; or 15-80 microns; or 15-70 microns; or 15-60microns; or 15-50 microns; or 15-40 microns; or 15-30 microns; or 15-20microns; or 20-100 microns; or 20-90 microns; or 20-80 microns; or 20-70microns; or 20-60 microns; or 20-50 microns; or 20-40 microns; or 20-30microns; or 30-100 microns; or 30-90 microns; or 30-80 microns; or 30-70microns; or 30-60 microns; or 30-50 microns; or 30-40 microns; or 40-100microns; or 40-90 microns; or 40-80 microns; or 40-70 microns; or 40-60microns; or 40-50 microns; or 50-100 microns; or 50-90 microns; or 50-80microns; or 50-70 microns; or 50-60 microns; or 60-100 microns; or 60-90microns; or 60-80 microns; or 60-70 microns; or 70-100 microns; or 70-90microns; or 70-80 microns; or 80-100 microns; or 80-90 microns; or 0.1microns; or 0.5 microns; or 1 microns; or 2 microns; or 3 microns; or 4microns; or 5 microns; or 8 microns; or 10 microns; or 15 microns; or 20microns; or 30 microns; or 40 microns; or 50 microns; or 60 microns; or70 microns; or 80 microns; or 100 microns. For example, in someembodiments, the composition provided herein is a particulatecomposition with an average particle size of 0.1-20 micron; or 0.1-15micron; or 0.1-10 micron; or 0.1-8 micron; or 0.1-5 micron; or 1-5micron; or 5-10 micron.

In some embodiments, the composition includes one or more differentsizes of the particles in the composition. In some embodiments, thecomposition includes two or more, or three or more, or four or more, orfive or more, or ten or more, or 20 or more, or 3-20, or 4-10 differentsizes of the particles in the composition. For example, the compositionmay include two or more, or three or more, or between 3-20 particlesranging from 0.1-10 micron, 10-50 micron, 50-100 micron, 100-200 micron,200-500 micron, 500-1000 micron, and/or sub-micron sizes of theparticles.

In some embodiments, the composition provided herein may includedifferent morphologies of the particles, such as, but not limited to,fine or disperse and large or agglomerated.

The bulk density of the composition in the powder form or after thesetting and/or hardening of the cement may vary. In some embodiments,the composition provided herein has a bulk density of between 75lb/ft³-170 lb/ft³; or between 75 lb/ft³-160 lb/ft³; or between 75lb/ft³-150 lb/ft³; or between 75 lb/ft³-140 lb/ft³; or between 75lb/ft³-130 lb/ft³; or between 75 lb/ft³-125 lb/ft³; or between 75lb/ft³-120 lb/ft³; or between 75 lb/ft³-110 lb/ft³; or between 75lb/ft³-100 lb/ft³; or between 75 lb/ft³-90 lb/ft³; or between 75lb/ft³-80 lb/ft³; or between 80 lb/ft³-170 lb/ft³; or between 80lb/ft³-160 lb/ft³; or between 80 lb/ft³-150 lb/ft³; or between 80lb/ft³-140 lb/ft³; or between 80 lb/ft³-130 lb/ft³; or between 80lb/ft³-125 lb/ft³; or between 80 lb/ft³-120 lb/ft³; or between 80lb/ft³-110 lb/ft³; or between 80 lb/ft³-100 lb/ft³; or between 80lb/ft³-90 lb/ft³; or between 90 lb/ft³-170 lb/ft³; or between 90lb/ft³-160 lb/ft³; or between 90 lb/ft³-150 lb/ft³; or between 90lb/ft³-140 lb/ft³; or between 90 lb/ft³-130 lb/ft³; or between 90lb/ft³-125 lb/ft³; or between 90 lb/ft³-120 lb/ft³; or between 90lb/ft³-110 lb/ft³; or between 90 lb/ft³-100 lb/ft³; or between 90lb/ft³-90 lb/ft³; or between 100 lb/ft³-170 lb/ft³; or between 100lb/ft³-160 lb/ft³; or between 100 lb/ft³-150 lb/ft³; or between 100lb/ft³-140 lb/ft³; or between 100 lb/ft³-130 lb/ft³; or between 100lb/ft³-125 lb/ft³; or between 100 lb/ft³-120 lb/ft³; or between 100lb/ft³-110 lb/ft³; or between 110 lb/ft³-170 lb/ft³; or between 110lb/ft³-160 lb/ft³; or between 110 lb/ft³-150 lb/ft³; or between 110lb/ft³-140 lb/ft³; or between 110 lb/ft³-130 lb/ft³; or between 110lb/ft³-125 lb/ft³; or between 110 lb/ft³-120 lb/ft³; or between 120lb/ft³-170 lb/ft³; or between 120 lb/ft³-160 lb/ft³; or between 120lb/ft³-150 lb/ft³; or between 120 lb/ft³-140 lb/ft³; or between 120lb/ft³-130 lb/ft³; or between 120 lb/ft³-125 lb/ft³; or between 130lb/ft³-170 lb/ft³; or between 130 lb/ft³-160 lb/ft³; or between 130lb/ft³-150 lb/ft³; or between 130 lb/ft³-140 lb/ft³; or between 140lb/ft³-170 lb/ft³; or between 140 lb/ft³-160 lb/ft³; or between 140lb/ft³-150 lb/ft³; or between 150 lb/ft³-170 lb/ft³; or between 150lb/ft³-160 lb/ft³; or between 160 lb/ft³-170 lb/ft³; or 75 lb/ft³; or 80lb/ft3; or 85 lb/ft³; or 90 lb/ft³; or 95 lb/ft³; or 100 lb/ft³; or 110lb/ft³; or 120 lb/ft³; or 130 lb/ft³; or 140 lb/ft³; or 150 lb/ft³; or160 lb/ft³; or 170 lb/ft³.

The surface area of the components making up the cement may vary. Insome embodiments, the compositions provided herein have an averagesurface area sufficient to provide for a liquid to solids ratio (asdescribed herein) upon combination with a liquid to produce a settablecomposition. In some embodiments, an average surface area ranges from0.5 m²/gm-50 m²/gm. The surface area may be determined using the surfacearea determination protocol described in Breunner, Emmit and Teller(BET) surface area analysis. In some embodiments, the compositionprovided herein has an average surface area of from 0.5 m²/gm-50 m²/gm;or from 0.5 m²/gm-45 m²/gm; or from 0.5 m²/gm-40 m²/gm; or from 0.5m²/gm-35 m²/gm; or from 0.5 m²/gm-30 m²/gm; or from 0.5 m²/gm-25 m²/gm;or from 0.5 m²/gm-20 m²/gm; or from 0.5 m²/gm-15 m²/gm; or from 0.5m²/gm-10 m²/gm; or from 0.5 m²/gm-5 m²/gm; or from 0.5 m²/gm-4 m²/gm; orfrom 0.5 m²/gm-2 m²/gm; or from 0.5 m²/gm-1 m²/gm; or from 1 m²/gm-50m²/gm; or from 1 m²/gm-45 m²/gm; or from 1 m²/gm-40 m²/gm; or from 1m²/gm-35 m²/gm; or from 1 m²/gm-30 m²/gm; or from 1 m²/gm-25 m²/gm; orfrom 1 m²/gm-20 m²/gm; or from 1 m²/gm-15 m²/gm; or from 1 m²/gm-10m²/gm; or from 1 m²/gm-5 m²/gm; or from 1 m²/gm-4 m²/gm; or from 1m²/gm-2 m²/gm; or from 2 m²/gm-50 m²/gm; or from 5 m²/gm-50 m²/gm; orfrom 8 m²/gm-50 m²/gm; or from 10 m²/gm-50 m²/gm; or from 15 m²/gm-50m²/gm; or from 20 m²/gm-50 m²/gm; or from 30 m²/gm-50 m²/gm; or from 40m²/gm-50 m²/gm; or 0.5 m²/gm; or 1 m²/gm; or 2 m²/gm; or 5 m²/gm; or 10m²/gm; or 15 m²/gm; or 20 m²/gm; or 30 m²/gm; or 40 m²/gm; or 50 m²/gm.In some embodiments, the composition provided herein includes a mix ofparticles, such as, but not limited to, two or more, three or more, orfour or more, or 5-10, or 10-20, or 1-20, or 1-50 particles withdifferent surface area.

In some embodiments, in the aspects and embodiments provided herein, thecomposition has a zeta potential of greater than −25 millivolts (mV).Zeta potential is the potential difference between the dispersion mediumand the stationary layer of fluid attached to the dispersed particle.The zeta potential indicates a degree of repulsion between adjacentsimilar particles in the dispersion. When the zeta potential is high,the particles may repel and resist aggregation resulting in highdispersion of the particles in the medium. When the zeta potential islow, the attraction may exceed repulsion causing the dispersion to breakand particles to flocculate. Without being bound by any theory, it isproposed that the high dispersion of the particles in the compositionsmay facilitate the SCM properties of the composition where the SCMcomposition may not flocculate readily and may be added to Portlandcement as SCM. The low dispersion of the particles in the compositionmay cause setting and hardening of the composition making the cementsuitable as the hydraulic cement. The low dispersion of the particles inthe composition may also cause setting and hardening of the compositionmaking the cement suitable as the self-cementing material. Thestabilizers may affect the surface charge and/or zeta potential of thecarbonate particles. The experimental techniques to determine the zetapotential are well known in the art and include, but are not limited to,electrophoresis such as microelectrophoresis and electrophoretic lightscattering.

In some embodiments, the aspects and embodiments provided herein, thecomposition includes a zeta potential of greater than −20 mV; or greaterthan −15 mV; or greater than −10 mV; or greater than −5 mV; or greaterthan −1 mV; or greater than 1 mV; or greater than 2 mV; or greater than3 mV; or greater than 5 mV; or greater than 10 mV; or greater than 15mV; or greater than 20 mV; or greater than 25 mV; or greater than 30 mV;or greater than 35 mV; or greater than 40 mV; or greater than 45 mV; orgreater than 50 mV; or less than 45 mV; or less than 40 mV; or less than35 mV; or less than 30 mV; or less than 25 mV; or less than 20 mV; orless than 15 mV; or less than 10 mV; or less than 5 mV; or less than 1mV; or less than −1 mV; or less than −5 mV; or less than −10 mV; or lessthan −20 mV; or less than −25 mV; or between +50 mV to −25 mV; orbetween +1 mV to −25 mV; or between −1 mV to −25 mV; or between −10 mVto −5 mV; or between −15 mV to −5 mV; or between −20 mV to −5 mV; orbetween −25 mV to −5 mV; or between +25 mV to −1 mV; or between +20 mVto −1 mV; or between +15 mV to −1 mV; or between +10 mV to −1 mV; orbetween +5 mV to −1 mV; or between +1 mV to −1 mV; or between −5 mV to−1 mV; or between −10 mV to −1 mV; or between −15 mV to −1 mV; orbetween −20 mV to −1 mV; or between −25 mV to −1 mV; or between 25 mV to5 mV; or between 20 mV to 5 mV; or between 15 mV to 5 mV; or between 10mV to 5 mV; or between 1 mV to 5 mV; or between −1 mV to +5 mV; orbetween −5 mV to +5 mV; or between 5 mV to 20 mV; or between 1 mV to 20mV; or between −1 mV to +20 mV; or between −5 mV to +20 mV; or between−10 mV to +20 mV; or between −15 mV to +20 mV; or between −20 mV to +20mV; or between −25 mV to +20 mV; or between 20 mV to 25 mV; or between15 mV to 25 mV; or between 10 mV to 25 mV; or between 5 mV to 25 mV; orbetween 1 mV to 25 mV; or between −1 mV to +25 mV; or between −5 mV to+25 mV; or between −10 mV to +25 mV; or between −15 mV to +25 mV; orbetween −20 mV to +25 mV. For example, in the aspects and embodimentsprovided herein, the composition includes a zeta potential of between 10mV to 45 mV; or between 15 mV to 45 mV; or between 20 mV to 45 mV; orbetween 25 mV to 45 mV; or between 30 mV to 45 mV; or between 35 mV to45 mV; or between 40 mV to 45 mV. In some embodiments, the compositionprovided herein includes a mix of particles with different zetapotential. For example, two or more, or three or more particles, or 3-20particles in the composition may have different zeta potentials.

In some embodiments, a ratio of calcium to carbonate in the compositionmay affect the zeta potential of the composition. In some embodiments, aratio of stabilizer with the metastable carbonate may affect the zetapotential of the composition. Without being limited by any theory, it isproposed that the higher ratio of calcium with the carbonate may resultin a higher zeta potential or a positive zeta potential, and the lowerratio of the calcium with the carbonate may result in a lower zetapotential or a negative zeta potential. In some embodiments, the ratioof calcium or calcium ion with the carbonate or the carbonate ion in thecomposition (calcium:carbonate) is greater than 1:1; or greater than1.5:1; or greater than 2:1; or greater than 2.5:1; or greater than 3:1;or greater than 3.5:1; or greater than 4:1; or greater than 4.5:1; orgreater than 5:1; or is in a range of 1:1 to 5:1; or is in a range of1.5:1 to 5:1; or is in a range of 2:1 to 5:1; or is in a range of 3:1 to5:1; or is in a range of 4:1 to 5:1; or is in a range of 1:1 to 4:1; oris in a range of 1.5:1 to 4:1; or is in a range of 2:1 to 4:1; or is ina range of 3:1 to 4:1; or is in a range of 1:1 to 3:1; or is in a rangeof 1.5:1 to 3:1; or is in a range of 2:1 to 3:1; or is in a range of 1:1to 2:1; or is in a range of 1.5:1 to 2:1; or is in a range of 1.5:1 to1:1; or is in a range of 1.2:1 to 1.8:1; or is 1:1; or is 1.5:1; or is2:1; or is 2.5:1; or is 3:1; or is 3.5:1; or is 4:1; or is 4.5:1; or is5:1. In some embodiments, the ratio of calcium:carbonate in thecomposition is 1.5:1, or 1:1, or 2:1.

In some embodiments, the ratio of carbonate or the carbonate ion withthe calcium or calcium ion in the composition (carbonate:calcium) isgreater than 1:1; or greater than 1.5:1; or greater than 2:1; or greaterthan 2.5:1; or greater than 3:1; or greater than 3.5:1; or greater than4:1; or greater than 4.5:1; or greater than 5:1; or is in a range of 1:1to 5:1; or is in a range of 1.5:1 to 5:1; or is in a range of 2:1 to5:1; or is in a range of 3:1 to 5:1; or is in a range of 4:1 to 5:1; oris in a range of 1:1 to 4:1; or is in a range of 1.5:1 to 4:1; or is ina range of 2:1 to 4:1; or is in a range of 3:1 to 4:1; or is in a rangeof 1:1 to 3:1; or is in a range of 1.5:1 to 3:1; or is in a range of 2:1to 3:1; or is in a range of 1:1 to 2:1; or is in a range of 1.5:1 to2:1; or is in a range of 1.5:1 to 1:1; or is 1:1; or is 1.5:1; or is2:1; or is 2.5:1; or is 3:1; or is 3.5:1; or is 4:1; or is 4.5:1; or is5:1. In some embodiments, the ratio of carbonate to calcium(carbonate:calcium) in the composition is 1.5:1, or 1:1, or 2:1.

In some embodiments, the composition of the invention includes a ratioof the carbonate to the hydroxide (carbonate:hydroxide) in a range of100:1; or 10:1 or 1:1.

In some embodiments, the compositions contain polymorphs of carbonatesin combination with bicarbonates, e.g., of divalent cations such ascalcium or magnesium; in some cases the composition containssubstantially all polymorphs of carbonates, or substantially allbicarbonates, or some ratio of polymorphs of carbonate to bicarbonate.The molar ratio of carbonates to bicarbonates may be any suitable ratio,such as carbonate:bicarbonate ratio of 500/1 to 100/1; 100/1 to 1/100,or 50/1 to 1/50, or 25/1 to 1/25, or 10/1 to 1/10, or 2/1 to 1/2, orabout 1/1, or substantially all carbonate or substantially allbicarbonate.

In some embodiments, when the compositions provided herein are derivedfrom a saltwater source, they may include one or more components thatare present in the saltwater source which may help in identifying thecompositions that come from the saltwater source. These identifyingcomponents and the amounts thereof are collectively referred to hereinas a saltwater source identifier or “markers”. For example, if thesaltwater source is sea water, identifying component that may be presentin the composition include, but are not limited to: chloride, sodium,sulfur, potassium, bromide, silicon, strontium and the like. Any suchsource-identifying or marker elements are generally present in smallamounts, e.g., in amounts of 20,000 ppm or less, such as amounts of 2000ppm or less. In certain embodiments, the marker compounds are strontiumor magnesium. The saltwater source identifier of the compositions mayvary depending on the particular saltwater source employed to producethe saltwater-derived composition. In some embodiments, the compositionis characterized by having a water source identifying carbonate tohydroxide compound ratio, where in certain embodiments thecarbonate:hydroxide ratio ranges from 100 to 1, such as 10 to 1 andincluding 1 to 1.

In some embodiments, the compositions provided herein further includenitrogen oxide, sulfur oxide, mercury, metal, derivative of any ofnitrogen oxide, sulfur oxide, mercury, and/or metal, or combinationthereof. The derivatives of nitrogen oxide and sulfur oxide include, butnot limited to, nitrates, nitrites, sulfates, and sulfites, etc. Themercury and/or the metal may be present in their derivatized form, suchas, oxides and/or hydroxides, or the mercury and/or the metal may beencapsulated or present in the composition of the invention inun-derivatized form. In some embodiments, the compositions providedherein further includes one or more additional components including, butare not limited to, blast furnace slag, fly ash, diatomaceous earth, andother natural or artificial pozzolans, silica fumes, limestone, gypsum,hydrated lime, air entrainers, retarders, waterproofers and coloringagents. These components may be added to modify the properties of thecement, e.g., to provide desired strength attainment, to provide desiredsetting times, etc. The amount of such components present in a givencomposition of the invention may vary, and in certain embodiments theamounts of these components range from 1 to 50% w/w, or 10% w/w to 50%w/w, such as 2 to 10% w/w.

In some embodiments, silica minerals may co-occur with the vateritecompositions of the invention. These compounds may be amorphous innature or crystalline. In certain embodiments, the silica may be in theform of opal-A, amorphous silica, typically found in chert rocks.Calcium magnesium carbonate silicate amorphous compounds may form,within crystalline regions of the polymorphs listed above.Non-carbonate, silicate minerals may also form. Sepiolite is a claymineral, a complex magnesium silicate, a typical formula for which isMg₄Si₆O₁₅(OH)₂.6H₂O. It can be present in fibrous, fine-particulate, andsolid forms. Silcate carbonate minerals may also form. Carletonite,KNa₄Ca₄CO₃)₄Si₈O₁₈ (F, OH).H₂O, Hydrated potassium sodium calciumcarbonate silicate, can form under these conditions. Like any member ofthe phyllosilicates subclass, carletonite's structure is layered withalternating silicate sheets and the potassium, sodium and calciumlayers. Unlike other phyllosilicates, carletonite's silicate sheets arecomposed of interconnected four and eight-member rings. The sheets canbe thought of as being like chicken wire with alternating octagon andsquare shaped holes. Both octagons and squares have a four fold symmetryand this is what gives carletonite its tetragonal symmetry; 4/m 2/m 2/m.Only carletonite and other members of the apophyllite group have thisunique interconnected four and eight-member ring structure.

In some embodiments, the compositions provided herein further includegeopolymers. As used herein, “geopolymers” are conventionally known inthe art and include chains or networks of mineral molecules that includealumina silica chains, such as, —Si—O—Si—O— siloxo, poly(siloxo);—Si—O—Al—O— sialate, poly(sialate); —Si—O—Al—O—Si—O— sialate-siloxo,poly(sialate-siloxo); —Si—O—Al—O—Si—O—Si—O— sialate-disiloxo,poly(sialate-disiloxo); —P—O—P—O— phosphate, poly(phosphate);—P—O—Si—O—P—O— phospho-siloxo, poly(phospho-siloxo); —P—O—Si—O—Al—O—P—O—phospho-sialate, poly(phospho-sialate); and —(R)—Si—O—Si—O—(R)organo-siloxo, poly-silicone. Geopolymers include, but are not limitedto, water-glass based geopolymer, kaolinite/hydrosodalite-basedgeopolymer, metakaolin MK-750-based geopolymer, calcium basedgeopolymer, rock-based geopolymer, silica-based geopolymer, fly-ashbased geopolymer, phosphate based geopolymer, and organic mineralgeopolymer. In some embodiments, the amount of geopolymer added to thecomposition of the invention is 1-50% by wt or 1-25% by wt or 1-10% bywt. The geopolymer can be blended into the composition of the inventionwhich can then be used as a hydraulic cement or SCM. The addition ofgeopolymer to the composition of the invention may decrease the settingtime and/or increase the compressive strength of cement when thecomposition in combination with water sets and hardens into the cement.

In some embodiments, the compositions provided herein further includePortland cement clinker, aggregate, or combination thereof. In someembodiments, the SCM compositions provided herein further includePortland cement clinker, aggregate, other supplementary cementitiousmaterial (SCM) (such as conventional SCM), or combination thereof. Insome embodiments, the other SCM is slag, fly ash, silica fume, orcalcined clay.

Typically, Portland cements are powder compositions produced by grindingPortland cement clinker (more than 90%), a limited amount of calciumsulfate which controls the set time, and up to 5% minor constituents (asallowed by various standards). As defined by the European StandardEN197.1, “Portland cement clinker is a hydraulic material which shallconsist of at least two-thirds by mass of calcium silicates (3CaO.SiO₂and 2CaO.SiO₂), the remainder consisting of aluminium- andiron-containing clinker phases and other compounds. The ratio ofCaO:SiO₂ shall not be less than 2.0. The magnesium content (MgO) shallnot exceed 5.0% by mass.” In certain embodiments, the Portland cementconstituent, as provided herein, is any Portland cement that satisfiesthe ASTM Standards and Specifications of C150 (Types I-VIII) of theAmerican Society for Testing of Materials (ASTM C50-StandardSpecification for Portland Cement). ASTM C150 covers eight types ofPortland cement, each possessing different properties, and usedspecifically for those properties.

In some embodiments, the composition provided herein may further includeOrdinary Portland Cement (OPC) or Portland cement clinker. The amount ofPortland cement component may vary and range from 10 to 95% w/w; or 10to 90% w/w; or 10 to 80% w/w; or 10 to 70% w/w; or 10 to 60% w/w; or 10to 50% w/w; or 10 to 40% w/w; or 10 to 30% w/w; or 10 to 20% w/w; or 20to 90% w/w; or 20 to 80% w/w; or 20 to 70% w/w; or 20 to 60% w/w; or 20to 50% w/w; or 20 to 40% w/w; or 20 to 30% w/w; or 30 to 90% w/w; or 30to 80% w/w; or 30 to 70% w/w; or 30 to 60% w/w; or 30 to 50% w/w; or 30to 40% w/w; or 40 to 90% w/w; or 40 to 80% w/w; or 40 to 70% w/w; or 40to 60% w/w; or 40 to 50% w/w; or 50 to 90% w/w; or 50 to 80% w/w; or 50to 70% w/w; or 50 to 60% w/w; or 60 to 90% w/w; or 60 to 80% w/w; or 60to 70% w/w; or 70 to 90% w/w; or 70 to 80% w/w. For example, thecomposition may include a blend of 75% OPC and 25% composition; or 80%OPC and 20% composition; or 85% OPC and 15% composition; or 90% OPC and10% composition; or 95% OPC and 5% composition. In some embodiments,such composition of the invention is an SCM.

In certain embodiments, the composition may further include anaggregate. Aggregate may be included in the composition to provide formortars which include fine aggregate and concretes which also includecoarse aggregate. The fine aggregates are materials that almost entirelypass through a Number 4 sieve (ASTM C 125 and ASTM C 33), such as silicasand. The coarse aggregate are materials that are predominantly retainedon a Number 4 sieve (ASTM C 125 and ASTM C 33), such as silica, quartz,crushed round marble, glass spheres, granite, limestone, calcite,feldspar, alluvial sands, sands or any other durable aggregate, andmixtures thereof. As such, the term “aggregate” is used broadly to referto a number of different types of both coarse and fine particulatematerial, including, but are not limited to, sand, gravel, crushedstone, slag, and recycled concrete. The amount and nature of theaggregate may vary widely. In some embodiments, the amount of aggregatemay range from 25 to 80%, such as 40 to 70% and including 50 to 70% w/wof the total composition made up of both the composition and theaggregate.

In some embodiments, the compositions further include a pH regulatingagent which may influence the pH of the fluid component of the settablecomposition produced from the composition or composition mixed withaggregates (to form concrete), upon combination of the composition withwater. Such pH regulating agents may provide for an alkaline environmentupon combination with water, e.g., where the pH of the hydrated cementis 12 or higher, such as 13 or higher, and including 13.5 or higher. Incertain embodiments, the pH regulating (i.e., modulating) agent is anoxide or hydroxide, e.g., calcium oxide, calcium hydroxide, magnesiumoxide or magnesium hydroxide. When present, such agents may be presentin amounts ranging from 1 to 10% w/w, such as 2 to 5% w/w.

In some embodiments, there is provided a settable composition preparedfrom the compositions provided herein. Such settable compositionsinclude, but not limited to, cement, concrete, and mortar. Settablecompositions may be produced by combining the composition with water orby combining the composition with an aggregate and water. The aggregatecan be a fine aggregate to prepare mortar, such as sand, or acombination of fine and coarse aggregate or coarse aggregate alone forconcrete. The composition, the aggregate, and the water may all be mixedat the same time or the composition may be pre-combined with theaggregate and the pre-combined mixture is then mixed with water. Thecoarse aggregate material for concrete mixes using the compositions mayhave a minimum size of about ⅜ inch and can vary in size from thatminimum to up to one inch or larger, including gradations between theselimits. Crushed limestone and other rocks, gravel, and the like are someexamples of the coarse aggregates. Finely divided aggregate is smallerthan ⅜ inch in size and may be graduated in much finer sizes down to200-sieve size or so. Ground limestone and other rocks, sand, and thelike are some examples of the fine aggregates. Fine aggregates may bepresent in both mortars and concretes of the invention. The weight ratioof the composition to the aggregate may vary, and in certain embodimentsranges from 1:10 to 4:10, such as 2:10 to 5:10 and including from55:1000 to 70:100.

The aqueous medium, such as, water, with which the dry components arecombined to produce the settable composition, may vary from pure waterto water that includes one or more solutes, additives, co-solvents,etc., as desired. The ratio of the aqueous medium:dry components oraqueous medium: composition of the invention is 0.1-10; or 0.1-8; or0.1-6; or 0.1-4; or 0.1-2; or 0.1-1; or 0.2-10; or 0.2-8; or 0.2-6; or0.2-4; or 0.2-2; or 0.2-1; or 0.3-10; or 0.3-8; or 0.3-6; or 0.3-4; or0.3-2; or 0.3-1; or 0.4-10; or 0.4-8; or 0.4-6; or 0.4-4; or 0.4-2; or0.4-1; or 0.5-10; or 0.5-8; or 0.5-6; or 0.5-4; or 0.5-2; or 0.5-1; or0.6-10; or 0.6-8; or 0.6-6; or 0.6-4; or 0.6-2; or 0.6-1; or 0.8-10; or0.8-8; or 0.8-6; or 0.8-4; or 0.8-2; or 0.8-1; or 1-10; or 1-8; or 1-6;or 1-4; or 1-2; or 0.1; or 0.5; or 1; or 2. In some embodiments, theratio is a weight ratio.

In certain embodiments, the compositions of the invention furtherinclude one or more admixtures. Admixtures may be added to concrete toprovide it with desirable characteristics or to modify properties of theconcrete to make it more readily useable or more suitable for aparticular purpose or for cost reduction. As is known in the art, anadmixture is any material or composition, other than the compositionprovided herein, aggregate and water; that is used as a component of theconcrete or mortar to enhance some characteristic or lower the cost,thereof. The amount of admixture that is employed may vary depending onthe nature of the admixture. In certain embodiments the amounts of thesecomponents range from 1 to 50% w/w, such as 2 to 10% w/w. Examples ofadmixtures are described in U.S. Pat. No. 7,922,809, which isincorporated herein by reference in its entirety.

In one aspect, there is provided a structure or a building materialcomprising the composition provided herein or the set and hardened formthereof. In some embodiments, the building material is formed from thecompositions provided herein. Examples of such structures or thebuilding materials include, but are not limited to, building, driveway,foundation, architectural cement, kitchen slab, furniture, pavement,road, bridges, motorway, overpass, parking structure, brick, block,wall, footing for a gate, fence, or pole, and combination thereof. Sincethese structures or building materials comprise and/or are produced fromthe compositions provided herein, they may include markers or componentsthat identify them as being obtained from carbon dioxide of fossil fuelorigin and/or being obtained from water having trace amounts of variouselements present in the initial salt water source, and/or being obtainedfrom a process employing stabilizers, as described herein. For example,where the mineral component of the cement component of the concrete isone that has been produced from sea water, the set product may contain aseawater marker profile of different elements in identifying amounts,such as magnesium, potassium, sulfur, boron, sodium, and chloride, etc.

In one aspect, there is provided a formed building material orpre-formed building material comprising the composition provided hereinor the set and hardened form thereof. In some embodiments, the formedbuilding material is formed from the compositions provided herein. Theformed building material may be a pre-cast building material, such as, apre-cast concrete product. The formed building materials and the methodsof making and using the formed building materials are described in U.S.Pat. No. 7,771,684, which is incorporated herein by reference in itsentirety. The formed building materials of the invention may varygreatly and include materials shaped (e.g., molded, cast, cut, orotherwise produced) into man-made structures with defined physicalshape, i.e., configuration. Formed building materials are distinct fromamorphous building materials (e.g., powder, paste, slurry, etc.) that donot have a defined and stable shape, but instead conform to thecontainer in which they are held, e.g., a bag or other container. Formedbuilding materials are also distinct from irregularly or impreciselyformed materials (e.g., aggregate, bulk forms for disposal, etc.) inthat formed building materials are produced according to specificationsthat allow for use of formed building materials in, for example,buildings. Formed building materials may be prepared in accordance withtraditional manufacturing protocols for such structures, with theexception that the composition provided herein is employed in makingsuch materials. In some embodiments, the formed building materials madefrom the composition provided herein have a compressive strength of atleast 14 MPa; or between about 14-100 MPa; or between about 14-45 MPa;or the compressive strength of the composition after setting, andhardening, as described herein. In some embodiments, the formed buildingmaterials made from the composition have a δ¹³C of less than −12‰; orless than −13‰; or less than −14‰; or less than −15‰; or from −15‰ to−80‰; or the δ¹³C of the composition, as described herein.

Some examples of the formed building materials include, but not limitedto, masonry units, brick, blocks, (e.g., concrete, cement, foundation,etc.), tile, construction panels, cement board, fiber-cement siding,drywall, conduit, basins, beam, column, concrete slab, acoustic barrier,and insulation material. In some embodiments, the formed buildingmaterial such as pre-cast concrete products include, but are not limitedto, bunker silo; cattle feed bunk; cattle grid; agricultural fencing;H-bunks; J-bunks; livestock slats; livestock watering troughs;architectural panel walls; cladding (brick); building trim; foundation;floors, including slab on grade; walls; double wall precast sandwichpanel; aqueducts; mechanically stabilized earth panels; box culverts;3-sided culverts; bridge systems; RR crossings; RR ties; soundwalls/barriers; Jersey barriers; tunnel segments; reinforced concretebox; utillity protection structure; hand holes; hollowcore product;light pole base; meter box; panel vault; pull box; telecom structure;transformer pad; transformer vault; trench; utility vault; utility pole;controlled environment vaults; underground vault; mausoleum; gravestone; coffin; haz mat storage container; detention vaults; catchbasins; manholes; aeration system; distribution box; dosing tank; drywell; grease interceptor; leaching pit; sand-oil/oil-water interceptor;septic tank; water/sewage storage tank; wetwells; fire cisterns;floating dock; underwater infrastructure; decking; railing; sea walls;roofing tiles; pavers; community retaining wall; res. retaining wall;modular block systems; and segmental retaining walls.

In some embodiments, there is provided synthetic rock or an aggregatecomprising the composition or the set and hardened form thereof. In someembodiments, the aggregate is made from the compositions providedherein. The aggregates and the methods of making and using theaggregates are described in U.S. Pat. No. 7,753,618, which isincorporated herein by reference in its entirety. The aggregate may beformed from hydraulic cement or SCM or self-cementing compositionprovided herein. In some embodiments, aggregates are formed, in whole orin part, from compositions that have been exposed to freshwater andallowed to harden into stable compounds, which may then be furtherprocessed, if necessary, to form particles as appropriate to the type ofaggregate desired. In some embodiments, aggregates are formed fromcompositions provided herein, that are exposed to conditions oftemperature and/or pressure that convert them into stable compounds.Further provided herein are structures, such as roadways, buildings,dams, and other manmade structures, containing the synthetic rock oraggregates made from the compositions provided herein.

In some embodiments, some or all the embodiments recited herein for thecomposition also apply to the aggregates made from the compositionsprovided herein.

Other products formed from the composition of the invention include, butare not limited to, non-cementitious compositions including paperproduct, polymer product, lubricant, adhesive, rubber product, chalk,asphalt product, paint, abrasive for paint removal, personal careproduct, cosmetic, cleaning product, personal hygiene product,ingestible product, agricultural product, soil amendment product,pesticide, environmental remediation product, and combination thereof.Such compositions have been described in U.S. Pat. No. 7,829,053, issuedNov. 9, 2010, which is incorporated herein by reference in its entirety.

II. Methods and Systems

Aspects of the invention include methods and systems for making thecomposition provided herein. The method to produce the compositionsprovided herein includes a source of carbon, a source of water, a sourceof alkalinity, a source of stabilizer, and a source for alkaline earthmetal ions, depending upon the materials used for the process. In oneaspect of the invention, there is provided a method for making thecomposition provided herein, by (a) contacting CO₂ from a CO₂ sourcewith a proton removing agent to form a solution; and (b) contacting thesolution with an alkaline earth-metal and stabilizer containing waterunder one or more conditions to make the composition provided herein. Inanother aspect of the invention, there is provided a method for making acomposition by (a) contacting CO₂ from a CO₂ source with a protonremoving agent to form a solution; and (b) contacting the solution withan alkaline earth-metal containing water under one or more conditions tomake the composition, wherein the composition includes a metastablecarbonate and a stabilizer. In some embodiments, the above describedmethod further includes contacting the stabilizer with the solutionbefore step (b). In some embodiments, the above described method furtherincludes contacting the stabilizer with the alkaline earth-metalcontaining water before step (b). In some embodiments, the abovedescribed method further includes contacting the stabilizer with thesolution simultaneously at step (b). In some embodiments, the abovedescribed method further includes contacting the stabilizer with thesolution after step (b). In some embodiments, the above described methodfurther includes contacting the stabilizer with the solution after step(b) but before dewatering.

In some embodiments, there are provided methods to optimize thestability of vaterite in a composition comprising vaterite andstabilizer, by optimizing the concentration of the stabilizer in thecomposition. In some embodiments, the stabilizer is as described herein.For example, in some embodiments, the stabilizer is sulfate ion such as,but not limited to, sulfate in sea water, alkali metal sulfate such as,sodium sulfate, alkaline earth metal sulfate, lignosulfate, orcombination thereof. In some embodiments, there are provided methods tooptimize the stability of vaterite in a composition comprising vateriteand stabilizer, by optimizing the concentration of the stabilizer in thecomposition between 0.1 wt % to 5 wt %. Aplicants have unexpectedly andsurprisingly found that by optimizing the concentration of thestabilizer during the precipitation process, the concentration of thestabilizer in the vaterite containing precipitate or the composition maybe optimized. The optimized concentration of the stabilizer in theprecipitate or the composition can then result in optimized stability ofthe vaterite in the precipitate or the composition.

For example, the precipitate or the composition comprising less than 1.5wt % stabilizer may produce a reactive vaterite that readily transformsto aragonite when it is combined with water. Such composition may besuitable for formed or pre-formed building material where it is desiredfor the composition to readily transform to aragonite in the mold andform the building material (e.g. brick etc.). In some embodiments, theprecipitate or the composition comprising between 0.5-2 wt % stabilizermay stabilize the vaterite for some period of time when the vaterite maytransform to aragonite or calcite. Such composition may be suitable forcementing purposes where the composition needs to be stable for extendedperiods but needs to convert to aragonite when combined with water. Insome embodiments, the precipitate or the composition comprising morethan 1 wt % stabilizer may stabilize the vaterite for extended periodsof time when the vaterite may not transform to aragonite or calcite.Such composition may be suitable for SCM purposes where the compositionneeds to be stable for extended periods of time and need not convert toaragonite when combined with water (may be acting as a filler).

In another aspect of the invention, there is provided a method formaking the composition provided herein, by (a) contacting CO₂ from a CO₂source with a proton removing agent to form a solution; (b) contactingthe solution with an alkaline earth-metal and stabilizer containingwater under one or more conditions to make the composition comprisingvaterite; and (c) activating vaterite containing composition. Thevaterite may be activated by methods described herein, e.g., mechanicalactivation, such as ball-milling or by chemical or nuclei activation,such as, by adding aragonite seed, inorganic additive or organicadditive. The activation of the vaterite facilitates the control ofaragonite formation upon addition of water to the composition.

Accordingly, in one aspect of the invention, there is provided a methodfor making the composition provided herein, by (a) contacting CO₂ with aproton removing agent to form a solution; (b) contacting the solutionwith an alkaline earth-metal and stabilizer containing water under oneor more conditions to make a composition comprising vaterite; (c)activating vaterite containing composition; and (d) controllingaragonite formation from the activated vaterite upon addition of waterto the composition.

In some embodiments, the vaterite containing composition is activated bynuclei activation, mechanical activation, chemical activation, orcombination thereof.

The mechanical activation of the vaterite containing compositionincludes modifying the surface of the vaterite by creating surfacedefects on vaterite. Such surface defects may be created by methods suchas ball-milling. The ball-milling process may grind the vateritecontaining composition in such a way that finer powder of the vateriteis formed. It is contemplated that the energy induced in vaterite bygrinding may be harnessed to form aragonite upon reaction of vateritewith water.

The nuclei activation of the vaterite containing composition may beinduced by adding an aragonite seed in the vaterite containingcomposition. The aragonite seed may induce aragonite formation duringthe dissolution-reprecipitation of the vaterite containing composition.The aragonite seed may also be induced in situ by thermal activation ofthe vaterite containing composition. For example, the vateritecontaining composition may be combined with water and then may be heatedfor a period of time such that aragonite seed may be formed in thecomposition. This aragonite seed that is formed in situ may facilitatearagonite formation during cementation.

In some embodiments, the activation of vaterite, as described herein,may induce aragonite formation or may facilitate control of thearagonite formation upon addition of water to the vaterite composition.In some embodiments, the activation of the vaterite in the cementitiouscomposition may affect the morphology, the linkage, and/or thecompressive strength of the aragonite after cementation. In someembodiments, the control of the aragonite formation includes, but notlimited to, rate of formation of aragonite, morphology of aragonite(e.g. needle shaped), and/or cross-linkage of aragonite. In someembodiments, the aragonite formation may result in one or more of betterlinkage or bonding, higher tensile strength, or higher impact fracturetoughness, after cementation of the cementitious composition.

The chemical activation of the vaterite containing composition may beinduced by adding the inorganic additive or organic additive, asdescribed herein in Example 5.

In another aspect, there is provided a method of forming a formedbuilding material, comprising activating a cementitious compositioncomprising vaterite; mixing water in the cementitious composition forcementation; pouring the cementitious composition in a mold; controllingaragonite formation upon cementation of the cementitious composition;and allowing the composition to set and harden in the mold to form aformed building material. The formed building material that can beformed by this method, are described herein.

As described herein, the method to produce the compositions providedherein includes carbon, water, alkalinity, and alkaline earth metalions, depending upon the materials used for the process. Below isprovided the description of the elements and their sources used in themethods and systems described herein.

Source of Carbon or CO₂

The CO₂ source may be a liquid, solid (e.g., dry ice) or gaseous CO₂source. In certain embodiments, the CO₂ source is a gaseous CO₂ source.This gaseous CO₂ is, in certain instances, a waste stream or productfrom an industrial plant. The nature of the industrial plant may vary inthese embodiments, where industrial plants of interest includes, but isnot limited to, power plants (e.g., as described in further detail inInternational Application No. PCT/US08/88318, titled, “Methods ofSequestring CO₂,” filed 24 Dec. 2008, the disclosure of which is hereinincorporated by reference), chemical processing plants, steel mills,paper mills, cement plants (e.g., as described in further detail in U.S.Provisional Application Ser. No. 61/088,340, the disclosure of which isherein incorporated by reference), and other industrial plants thatproduce CO₂ as a byproduct. By waste stream is meant a stream of gas (oranalogous stream) that is produced as a byproduct of an active processof the industrial plant. The gaseous stream may be substantially pureCO₂ or a multi-component gaseous stream that includes CO₂ and one ormore additional gases. Multi-component gaseous streams (containing CO₂)that may be employed as a CO₂ source in embodiments of the subjectmethods include both reducing, e.g., syngas, shifted syngas, naturalgas, and hydrogen and the like, and oxidizing condition streams, e.g.,flue gases from combustion. Exhaust gases containing NOx, SOx, VOCs,particulates and Hg would incorporate these compounds along with thecarbonate in the precipitated product. Particular multi-componentgaseous streams of interest include, but not limited to, oxygencontaining combustion power plant flue gas, turbo charged boiler productgas, coal gasification product gas, shifted coal gasification productgas, anaerobic digester product gas, wellhead natural gas stream,reformed natural gas or methane hydrates, and the like.

Thus, the waste streams may be produced from a variety of differenttypes of industrial plants. Suitable waste streams include wastestreams, such as, flue gas, produced by industrial plants that combustfossil fuels (e.g., coal, oil, natural gas) or anthropogenic fuelproducts of naturally occurring organic fuel deposits (e.g., tar sands,heavy oil, oil shale, etc.). In some embodiments, a waste streamsuitable for systems and methods provided herein is sourced from acoal-fired power plant, such as a pulverized coal power plant, asupercritical coal power plant, a mass burn coal power plant, afluidized bed coal power plant. In some embodiments, the waste stream issourced from gas or oil-fired boiler and steam turbine power plants, gasor oil-fired boiler simple cycle gas turbine power plants, or gas oroil-fired boiler combined cycle gas turbine power plants. In someembodiments, waste streams produced by power plants that combust syngas(i.e., gas that is produced by the gasification of organic matter, forexample, coal, biomass, etc.) are used. In some embodiments, wastestreams from integrated gasification combined cycle (IGCC) plants areused. In some embodiments, waste streams produced by Heat Recovery SteamGenerator (HRSG) plants are used to produce compositions in accordancewith systems and methods provided herein.

Waste streams produced by cement plants are also suitable for systemsand methods provided herein. Cement plant waste streams include wastestreams from both wet process and dry process plants, which plants mayemploy shaft kilns or rotary kilns, and may include pre-calciners. Theseindustrial plants may each burn a single fuel, or may burn two or morefuels sequentially or simultaneously.

In some embodiments, the source of carbon may be synthetic or naturallyoccurring carbonate, such as sodium carbonate, or limestone.

Source of Water

As reviewed above, “saltwater” is employed in its conventional sense toinclude a number of different types of aqueous fluids other than freshwater, where the term “saltwater” includes brackish water, sea water andbrine (including man-made brines, e.g., geothermal plant wastewaters,desalination waste waters, etc), as well as other salines having asalinity that is greater than that of freshwater. Brine is watersaturated or nearly saturated with salt and has a salinity that is 50ppt (parts per thousand) or greater. Brackish water is water that issaltier than fresh water, but not as salty as seawater, having asalinity ranging from 0.5 to 35 ppt. Seawater is water from a sea orocean and has a salinity ranging from 35 to 50 ppt.

The saltwater source from which the composition is derived may be anaturally occurring source, such as a sea, ocean, lake, swamp, estuary,lagoon, etc., or a man-made source. The compositions provided herein maybe produced by precipitation from alkaline-earth-metal-containing water,such as, a saltwater, or a freshwater with added alkaline earth metalions. The saltwater employed in methods may vary.

In some embodiments, the water employed in the invention may be amineral rich, e.g., calcium and/or magnesium rich, freshwater source. Insome embodiments, calcium rich waters may be combined with magnesiumsilicate minerals, such as olivine or serpentine. The acidity in thesolution, due to the addition of carbon dioxide to form carbonic acid,may dissolve the magnesium silicate, leading to the formation of calciummagnesium silicate carbonate compounds.

In some embodiments, the compositions are obtained from saltwater, e.g.,by treating a volume of a saltwater in a manner sufficient to producethe desired composition from the initial volume of saltwater. In certainembodiments, the compositions provided herein are derived from saltwaterby precipitating them from the saltwater. In certain embodiments, thecompositions provided herein are separated in a solid form from thesaltwater. In some embodiments, the compositions provided herein may bemore stable in saltwater than in freshwater, such that they may beviewed as saltwater metastable compositions.

In some embodiments, the water may be obtained from the power plant thatis also providing the gaseous waste stream. For example, in water cooledpower plants, such as seawater cooled power plants, water that has beenemployed by the power plant may then be sent to the precipitation systemand employed as the water in the precipitation reaction. In certain ofthese embodiments, the water may be cooled prior to entering theprecipitation reactor.

Source of Alkalinity

In some embodiments, the CO₂ from the source of CO₂ is contacted with aproton removing agent. The contact may result in a solution containingcarbonic acid, bicarbonate, carbonate, hydronium, etc. The protonremoving agent may facilitate removal of protons from carbonic acid toform various species, e.g. bicarbonate, carbonate, hydronium, etc. inthe solution. The terms “source of alkalinity” or “proton removingagents” or “pH raising or elevating agent,” or “base,” are usedinterchangeably herein. As protons are removed, more CO₂ goes intosolution. In some embodiments, the solution, obtained after contactingthe CO₂ with the proton removing agent, is then contacted with thealkaline-earth metal ions to cause precipitation of the carbonateprecipitate. In some embodiments, proton-removing agents and/or methodsare used while contacting a divalent cation-containing aqueous solutionwith CO₂ to increase CO₂ absorption in one phase of the precipitationreaction, wherein the pH may remain constant, increase, or evendecrease, followed by a rapid removal of protons (e.g., by addition of abase) to cause rapid precipitation of carbonate-containing precipitationmaterial. Protons may be removed from the various species (e.g. carbonicacid, bicarbonate, hydronium, etc.) by any suitable approach, including,but not limited to, use of naturally occurring proton-removing agents,use of microorganisms and fungi, use of synthetic chemicalproton-removing agents, recovery of man-made waste streams, and usingelectrochemical means.

Naturally occurring proton-removing agents encompass any proton-removingagents that can be found in the wider environment that may create orhave a basic local environment. Some embodiments provide for naturallyoccurring proton-removing agents including minerals that create basicenvironments upon addition to solution. Such minerals include, but arenot limited to, lime (CaO); periclase (MgO); iron hydroxide minerals(e.g., goethite and limonite); and volcanic ash. Methods for digestionof such minerals and rocks including such minerals are well known in theart.

Many minerals provide sources of divalent cations and, in addition, someminerals are sources of base. Mafic and ultramafic minerals such asolivine, serpentine, and any other suitable mineral may be dissolvedusing any convenient protocol. Dissolution may be accelerated byincreasing surface area, such as by milling by conventional means or by,e.g., jet milling, as well as by use of, e.g., ultrasonic techniques. Inaddition, mineral dissolution may be accelerated by exposure to acid orbase. Metal silicates (e.g., magnesium silicates) and other mineralsincluding cations of interest may be dissolved, e.g., in acid (e.g., HClsuch as HCl from an electrochemical process) to produce, for example,magnesium and other metal cations for use in precipitation material,and, subsequently, compositions of the invention. In some embodiments,magnesium silicates and other minerals may be digested or dissolved inan aqueous solution that has become acidic due to the addition of carbondioxide and other components of waste gas (e.g., combustion gas).Alternatively, other metal species such as metal hydroxide (e.g.,Mg(OH)₂, Ca(OH)₂) may be made available for use in aggregate bydissolution of one or more metal silicates (e.g., olivine andserpentine) with aqueous alkali hydroxide (e.g., NaOH) or any othersuitable caustic material. Any suitable concentration of aqueous alkalihydroxide or other caustic material may be used to decompose metalsilicates, including highly concentrated and very dilute solutions. Theconcentration (by weight) of an alkali hydroxide (e.g., NaOH) insolution may be, for example, from 30% to 80% and from 70% to 20% water.Advantageously, metal silicates and the like digested with aqueousalkali hydroxide may be used directly to produce precipitation material,and, subsequently, aggregate from a waste gas stream. In addition, basevalue from the precipitation reaction mixture may be recovered andreused to digest additional metal silicates and the like.

Some embodiments provide for using naturally alkaline bodies of water asnaturally occurring proton-removing agents. Examples of naturallyalkaline bodies of water include, but not limited to, surface watersources (e.g. alkaline lakes such as Mono Lake in California) and groundwater sources (e.g. basic aquifers such as the deep geologic alkalineaquifers located at Searles Lake in California). Other embodimentsprovide for use of deposits from dried alkaline bodies of water such asthe crust along Lake Natron in Africa's Great Rift Valley.

In some embodiments, organisms that excrete basic molecules or solutionsin their normal metabolism are used as proton-removing agents. Examplesof such organisms are fungi that produce alkaline protease (e.g., thedeep-sea fungus Aspergillus ustus with an optimal pH of 9) and bacteriathat create alkaline molecules (e.g., cyanobacteria such as Lyngbya sp.from the Atlin wetland in British Columbia, which increases pH from abyproduct of photosynthesis). In some embodiments, organisms are used toproduce proton-removing agents, wherein the organisms (e.g., Bacilluspasteurii, which hydrolyzes urea to ammonia) metabolize a contaminant(e.g. urea) to produce proton-removing agents or solutions includingproton-removing agents (e.g., ammonia, ammonium hydroxide). In someembodiments, organisms are cultured separately from the precipitationreaction mixture, wherein proton-removing agents or solution includingproton-removing agents are used for addition to the precipitationreaction mixture. In some embodiments, naturally occurring ormanufactured enzymes are used in combination with proton-removing agentsto invoke precipitation of precipitation material. Carbonic anhydrase,which is an enzyme produced by plants and animals, acceleratestransformation of carbonic acid to bicarbonate in aqueous solution.

Chemical agents for effecting proton removal generally refer tosynthetic chemical agents that are produced in large quantities and arecommercially available. For example, chemical agents for removingprotons include, but not limited to, hydroxides, organic bases, superbases, oxides, ammonia, and carbonates. Hydroxides include chemicalspecies that provide hydroxide anions in solution, including, forexample, sodium hydroxide (NaOH), potassium hydroxide (KOH), calciumhydroxide (Ca(OH)₂), or magnesium hydroxide (Mg(OH)₂). Organic bases arecarbon-containing molecules that are generally nitrogenous basesincluding primary amines such as methyl amine, secondary amines such asdiisopropylamine, tertiary such as diisopropylethylamine, aromaticamines such as aniline, heteroaromatics such as pyridine, imidazole, andbenzimidazole, and various forms thereof. In some embodiments, anorganic base selected from pyridine, methylamine, imidazole,benzimidazole, histidine, and a phophazene is used to remove protonsfrom various species (e.g., carbonic acid, bicarbonate, hydronium, etc.)for precipitation of precipitation material. In some embodiments,ammonia is used to raise pH to a level sufficient to precipitateprecipitation material from a solution of divalent cations and anindustrial waste stream. Super bases suitable for use as proton-removingagents include sodium ethoxide, sodium amide (NaNH₂), sodium hydride(NaH), butyl lithium, lithium diisopropylamide, lithium diethylamide,and lithium bis(trimethylsilyl)amide. Oxides including, for example,calcium oxide (CaO), magnesium oxide (MgO), strontium oxide (SrO),beryllium oxide (BeO), and barium oxide (BaO) are also suitableproton-removing agents that may be used. Carbonates for use in theinvention include, but are not limited to, sodium carbonate.

In addition to including cations of interest and other suitable metalforms, waste streams from various industrial processes may provideproton-removing agents. Such waste streams include, but are not limitedto, mining wastes; fossil fuel burning ash (e.g., combustion ash such asfly ash, bottom ash, boiler slag); slag (e.g. iron slag, phosphorousslag); cement kiln waste; oil refinery/petrochemical refinery waste(e.g. oil field and methane seam brines); coal seam wastes (e.g. gasproduction brines and coal seam brine); paper processing waste; watersoftening waste brine (e.g., ion exchange effluent); silicon processingwastes; agricultural waste; metal finishing waste; high pH textilewaste; and caustic sludge. Mining wastes include any wastes from theextraction of metal or another precious or useful mineral from theearth. In some embodiments, wastes from mining are used to modify pH,wherein the waste is selected from red mud from the Bayer aluminumextraction process; waste from magnesium extraction from sea water(e.g., Mg(OH)₂ such as that found in Moss Landing, Calif.); and wastesfrom mining processes involving leaching. For example, red mud may beused to modify pH as described in U.S. Provisional Patent ApplicationNo. 61/161,369, titled, “Neutralizing Industrial Wastes Utilizing CO₂And a Divalent Cation Solution”, filed 18 Mar. 2009, which is herebyincorporated by reference in its entirety. Fossil fuel burning ash,cement kiln dust, and slag, collectively waste sources of metal oxides,further described in U.S. patent application Ser. No. 12/486,692,titled, “Methods And Systems For Utilizing Waste Sources Of MetalOxides,” filed 17 Jun. 2009, the disclosure of which is incorporatedherein in its entirety, may be used in alone or in combination withother proton-removing agents to provide proton-removing agents for theinvention. Agricultural waste, either through animal waste or excessivefertilizer use, may contain potassium hydroxide (KOH) or ammonia (NH₃)or both. As such, agricultural waste may be used in some embodimentsprovided herein as a proton-removing agent. This agricultural waste isoften collected in ponds, but it may also percolate down into aquifers,where it can be accessed and used.

Where desired, the pH of the water is raised using any convenient and/orsuitable approach. In certain embodiments, a pH raising agent may beemployed, where examples of such agents include oxides, hydroxides(e.g., sodium hydroxide, potassium hydroxide, brucite), carbonates (e.g.sodium carbonate), coal ash, naturally occurring mineral, and the like.The amount of pH elevating agent that is added to the saltwater sourcewill depend on the particular nature of the agent and the volume ofsaltwater being modified, and will be sufficient to raise the pH of thesalt water source to the desired value. Alternatively, the pH of thesaltwater source can be raised to the desired level by electrolysis ofthe water.

One such approach can be to use the coal ash from a coal-fired powerplant, which contains many oxides, to elevate the pH of sea water. Othercoal processes, like the gasification of coal, to produce syngas, alsoproduce hydrogen gas and carbon monoxide, and may serve as a source ofhydroxide as well. Some naturally occurring minerals, such as,serpentine contain hydroxide, and can be dissolved, yielding a hydroxidesource. The amount of pH elevating agent that is added to the water maydepend on the particular nature of the agent and the volume of saltwaterbeing modified, and may be sufficient to raise the pH of the water tothe desired value. Alternatively, the pH of the saltwater source can beraised to the desired level by electrolysis of the water. Whereelectrolysis is employed, a variety of different protocols may be taken,such as use of the Mercury cell process (also called the Castner-Kellnerprocess); the Diaphragm cell process and the membrane cell process.Where desired, byproducts of the hydrolysis product, e.g., H₂, sodiummetal, etc. may be harvested and employed for other purposes, asdesired.

Electrochemical methods are another means to remove protons from variousspecies in a solution, either by removing protons from solute (e.g.,deprotonation of carbonic acid or bicarbonate) or from solvent (e.g.,deprotonation of hydronium or water). Deprotonation of solvent mayresult, for example, if proton production from CO₂ dissolution matchesor exceeds electrochemical proton removal from solute molecules. In someembodiments, low-voltage electrochemical methods are used to removeprotons, for example, as CO₂ is dissolved in the precipitation reactionmixture or a precursor solution to the precipitation reaction mixture(i.e., a solution that may or may not contain divalent cations).

In some embodiments, CO₂ dissolved in an aqueous solution that does notcontain divalent cations is treated by a low-voltage electrochemicalmethod to remove protons from carbonic acid, bicarbonate, hydronium, orany species or combination thereof resulting from the dissolution ofCO₂. A low-voltage electrochemical method operates at an average voltageof 2, 1.9, 1.8, 1.7, or 1.6 V or less, such as 1.5, 1.4, 1.3, 1.2, 1.1 Vor less, such as 1 V or less, such as 0.9 V or less, 0.8 V or less, 0.7V or less, 0.6 V or less, 0.5 V or less, 0.4 V or less, 0.3 V or less,0.2 V or less, or 0.1 V or less. Low-voltage electrochemical methodsthat do not generate chlorine gas are convenient for use in systems andmethods of the invention. Low-voltage electrochemical methods to removeprotons that do not generate oxygen gas are also convenient for use insystems and methods of the invention. In some embodiments, low-voltageelectrochemical methods generate hydrogen gas at the cathode andtransport it to the anode where the hydrogen gas is converted toprotons. Electrochemical methods that do not generate hydrogen gas mayalso be convenient. In some embodiments, electrochemical processes toremove protons do not generate a gas at the anode. In some instances,electrochemical methods to remove protons do not generate any gaseousby-byproduct.

Electrochemical methods for effecting proton removal are furtherdescribed in U.S. Pat. No. 7,887,694; U.S. Pat. No. 7,790,012;International Patent Application No. PCT/US08/088242, titled, “LOWENERGY ELECTROMECHANICAL HYDROXIDE SYSTEM AND METHOD,” filed 23 Dec.2008; International Patent Application No. PCT/US09/32301, titled,“LOW-ENERGY ELECTROCHEMICAL BICARBONATE ION SOLUTION,” filed 28 Jan.2009; International Patent Application No. PCT/US09/48511, titled,“LOW-ENERGY 4-CELL ELECTROCHEMICAL SYSTEM WITH CARBON DIOXIDE GAS,”filed 24 Jun. 2009, and U.S. Provisional Patent Application No.61/617,390, filed Mar. 29, 2012, each of which are incorporated hereinby reference in their entireties.

Low voltage electrochemical processes may produce hydroxide at thecathode and protons at the anode or hydroxide at the cathode andoxidized metal ions at the anode, such as in U.S. Provisional PatentApplication No. 61/617,390, filed Mar. 29, 2012, where such processesutilize a salt containing chloride, e.g. NaCl, a product of the processwill be NaOH. In some embodiments, electrochemical methods may be usedto produce caustic molecules (e.g., hydroxide) through, for example, thechlor-alkali process, or modification thereof. Electrodes (i.e.,cathodes and anodes) may be present in the apparatus containing thedivalent cation-containing aqueous solution or gaseous wastestream-charged (e.g., CO₂-charged) solution, and a selective barrier,such as a membrane, may separate the electrodes. Electrochemical systemsand methods for removing protons may produce by-products (e.g.,hydrogen) that may be harvested and used for other purposes. Additionalelectrochemical approaches that may be used in systems and methods ofthe invention include, but are not limited to, those described in U.S.patent application Ser. No. 12/503,557, titled, “CO₂ UTILIZATION INELECTROCHEMICAL SYSTEMS,” filed 15 Jul. 2009, the disclosures of whichare herein incorporated by reference in their entirety.

Combinations of the above mentioned sources of proton removal may beemployed. One such combination is the use of a microorganisms andelectrochemical systems. Combinations of microorganisms andelectrochemical systems include microbial electrolysis cells, includingmicrobial fuel cells, and bio-electrochemically assisted microbialreactors. In such microbial electrochemical systems, microorganisms(e.g. bacteria) are grown on or very near an electrode and in the courseof the metabolism of material (e.g. organic material) electrons aregenerated that are taken up by the electrode.

Additives other than pH elevating agents may also be introduced into thewater in order to influence the nature of the precipitate that isproduced. As such, certain embodiments of the methods include providingan additive in water before or during the time when the water issubjected to the precipitation conditions. Certain calcium carbonatepolymorphs can be favored by trace amounts of certain additives, suchas, but are not limited to, lanthanum as lanthanum chloride, transitionmetals, iron, nickel, and the like. For instance, iron may favor theformation of disordered dolomite (protodolomite).

In some embodiments, the source of alkalinity is bicarbonate, carbonate,or a mixture of NaOH and carbon dioxide, and the alkaline solution is a“high carbonate” alkaline solution. By “high carbonate” alkalinesolution is meant an aqueous composition which possesses carbonate in asufficient amount so as to remove one or more protons fromproton-containing species in solution such that carbonic acid isconverted to bicarbonate. As such, the amount of carbonate present inalkaline solutions of the invention may be 5,000 ppm or greater, such as10,000 ppm greater, such as 25,000 ppm or greater, such as 50,000 ppm orgreater, such as 75,000 ppm or greater, including 100,000 ppm orgreater.

Source of Cations, Such as, Alkaline Earth Metals

The source of cations, such as sodium, potassium, or alkaline earthmetal ions etc., is any aqueous medium containing alkaline earth metals,such as, but are not limited to, calcium, magnesium, strontium, barium,etc. or combination thereof. In some embodiments, the alkaline earthmetal is calcium, magnesium, or combination thereof and the source ofalkaline earth metal is any aqueous medium containing calcium, magnesiumor combination thereof. In some embodiments, alkaline earth metal sourceis also the source of water and/or source of alkalinity, as describedherein. For example, the aqueous solution of alkaline earth metal ionsmay comprise cations derived from freshwater, brackish water, seawater,or brine (e.g., naturally occurring subterranean brines or anthropogenicsubterranean brines such as geothermal plant wastewaters, desalinationplant waste waters), as well as other salines having a salinity that isgreater than that of freshwater, any of which may be naturally occurringor anthropogenic.

Divalent cations (e.g., alkaline earth metal cations such as Ca²⁺ andMg²⁺), which are useful for producing precipitation material of theinvention, may be found in industrial wastes, seawater, brines, hardwater, minerals, and many other suitable sources.

In some locations, industrial waste streams from various industrialprocesses provide for convenient sources of cations (as well as in somecases other materials useful in the process, e.g., metal hydroxide).Such waste streams include, but are not limited to, mining wastes;fossil fuel burning ash (e.g., fly ash, bottom ash, boiler slag); slag(e.g., iron slag, phosphorous slag); cement kiln waste (e.g., cementkiln dust); oil refinery/petrochemical refinery waste (e.g., oil fieldand methane seam brines); coal seam wastes (e.g., gas production brinesand coal seam brine); paper processing waste; water softening wastebrine (e.g., ion exchange effluent); silicon processing wastes;agricultural waste; metal finishing waste; high pH textile waste; andcaustic sludge.

In some locations, a convenient source of cations for use in systems andmethods provided herein is water (e.g., an aqueous solution includingcations such as seawater or subterranean brine), which may varydepending upon the particular location at which the invention ispracticed. Suitable aqueous solutions of cations that may be usedinclude solutions including one or more divalent cations, e.g., alkalineearth metal cations such as Ca²⁺ and Mg²⁺. In some embodiments, theaqueous source of cations comprises alkaline earth metal cations. Insome embodiments, the alkaline earth metal cations include calcium,magnesium, or a mixture thereof. In some embodiments, the aqueoussolution of cations comprises calcium in amounts ranging from 50 to50,000 ppm, 50 to 40,000 ppm, 50 to 20,000 ppm, 100 to 10,000 ppm, 200to 5000 ppm, or 400 to 1000 ppm, or 10,000 to 50,000 ppm, or 20,000 to50,000 ppm, or 20,000 to 30,000 ppm.

In some embodiments, mineral rich freshwater may be a convenient sourceof cations (e.g., cations of alkaline earth metals such as Ca²⁺ andMg²⁺). Any of a number of suitable freshwater sources may be used,including freshwater sources ranging from sources relatively free ofminerals to sources relatively rich in minerals. Mineral-rich freshwatersources may be naturally occurring, including any of a number of hardwater sources, lakes, or inland seas. Some mineral-rich freshwatersources such as alkaline lakes or inland seas (e.g., Lake Van in Turkey)also provide a source of pH-modifying agents. Mineral-rich freshwatersources may also be anthropogenic. For example, a mineral-poor (soft)water may be contacted with a source of cations such as alkaline earthmetal cations (e.g., Ca²⁺, Mg²⁺, etc.) to produce a mineral-rich waterthat is suitable for methods and systems described herein. Cations orprecursors thereof (e.g., salts, minerals) may be added to freshwater(or any other type of water described herein) using any convenientprotocol (e.g., addition of solids, suspensions, or solutions). In someembodiments, divalent cations selected from Ca²⁺ and Mg²⁺ are added tofreshwater. In some embodiments, monovalent cations selected from Na⁺and K⁺ are added to freshwater. In some embodiments, freshwaterincluding Ca²⁺ is combined with magnesium silicates (e.g., olivine orserpentine), or products or processed forms thereof, yielding a solutionincluding calcium and magnesium cations.

Many minerals provide sources of cations and, in addition, some mineralsare sources of base. Divalent cation-containing minerals include maficand ultramafic minerals such as olivine, serpentine, and other suitableminerals, which may be dissolved using any convenient protocol. In oneembodiment, cations such as calcium may be provided for methods andcompositions of this invention from feldspars such as anorthite. Cationsmay be obtained directly from mineral sources or from subterraneanbrines, high in calcium or other divalent cations. Other minerals suchas wollastonite may also be used. Dissolution may be accelerated byincreasing surface area, such as by milling by conventional means or by,for example, jet milling, as well as by use of, for example, ultrasonictechniques. In addition, mineral dissolution may be accelerated byexposure to acid or base.

Metal silicates (e.g., magnesium silicates) and other minerals includingcations of interest may be dissolved, for example, in an acid such asHCl (optionally from an electrochemical process) to produce, forexample, magnesium and other metal cations for use in compositionsprovided herein. In some embodiments, magnesium silicates and otherminerals may be digested or dissolved in an aqueous solution that hasbecome acidic due to the addition of carbon dioxide and other componentsof waste gas (e.g., combustion gas). Alternatively, other metal speciessuch as metal hydroxide (e.g., Mg(OH)₂, Ca(OH)₂) may be made availablefor use by dissolution of one or more metal silicates (e.g., olivine andserpentine) with aqueous alkali hydroxide (e.g., NaOH) or any othersuitable caustic material. Any suitable concentration of aqueous alkalihydroxide or other caustic material may be used to decompose metalsilicates, including highly concentrated and very dilute solutions. Theconcentration (by weight) of an alkali hydroxide (e.g., NaOH) insolution may be, for example, from 30% to 80% (w/w).

Brines

As used herein, “brines” includes synthetic brines or naturallyoccurring brines, such as, but are not limited to subterranean brines.The brines may provide the source of water, the source of alkaline earthmetal ions, the source of carbon or carbonate, the source of alkalinity,or combinations thereof.

In some embodiments the subterranean brines of this invention may be aconvenient source for divalent cations, monovalent cations, protonremoving agents, or any combination thereof. The subterranean brine thatis employed in embodiments of the invention may be from any convenientsubterranean brine source. “Subterranean brine” is employed in itsconventional sense to include naturally occurring or anthropogenic,saline compositions obtained from a geological location. The geologicallocation of the subterranean brine can be found below ground(subterranean geological location), on the surface, or subsurface of thelakes. Concentrated aqueous saline composition includes an aqueoussolution which has a salinity of 10,000 ppm total dissolved solids (TDS)or greater, such as 20,000 ppm TDS or greater and including 50,000 ppmTDS or greater. Subterranean geological location includes a geologicallocation which is located below ground level, such as, a solid-fluidinterface of the Earth's surface, such as a solid-gas interface as foundon dry land where dry land meets the Earth's atmosphere, as well as aliquid-solid interface as found beneath a body of surface water (e.g.,lack, ocean, stream, etc) where solid ground meets the body of water(where examples of this interface include lake beds, ocean floors, etc).For example, the subterranean location can be a location beneath land ora location beneath a body of water (e.g., oceanic ridge). For example, asubterranean location may be a deep geological alkaline aquifer or anunderground well located in the sedimentary basins of a petroleum field,a subterranean metal ore, a geothermal field, or an oceanic ridge, amongother underground locations.

Brines may be concentrated waste streams from wastewater treatmentplants. In some embodiments, brines of this invention may be waterresulting from dissolution of mineral sources (e.g., oil and gasexploration or extraction) that has been concentrated or otherwisetreated. The waste streams from underground sources such as gas orpetroleum mining may contain hydrocarbons, carbonates, cations oranions. Treatment of these waste streams to reduce hydrocarbons and thewater volume may result in an aqueous mixture rich in carbonates,salinity, alkalinity or any combination thereof. This aqueous mixturemay be used to sequester carbon dioxide or may be used to precipitatehydrated carbon species such as carbonic acid, bicarbonate, orcarbonates. Subterranean brines may include, but are not limited to,oil-field brines, basinal brines, basinal water, pore water, formationwater, and deep sea hypersaline waters, among others.

Subterranean brines of the invention may be subterranean aqueous salinecompositions and in some embodiments, may have circulated throughcrustal rocks and become enriched in substances leached from thesurrounding mineral. As such, the composition of subterranean brines mayvary. In some embodiments, the subterranean brines provide a source ofcations. The cations may be monovalent cations, such as Na⁺, K⁺, etc.The cations may also be divalent cations, such as Ca²⁺, Mg²⁺, Sr²⁺, Ba²⁺Mn²⁺, Zn²⁺, Fe²⁺, etc. In some instances, the divalent cations of thesubterranean brine are alkaline earth metal cations, e.g., Ca²⁺, Mg²⁺.Subterranean brines of interest may have Ca²⁺ present in amounts thatvary, ranging from 50 to 100,000 ppm, such as 100 to 75,000 ppm,including 500 to 50,000 ppm, for example 1000 to 25,000 ppm.Subterranean brines of interest may have Mg²⁺ present in amounts thatvary, ranging from 50 to 25,000 ppm, such as 100 to 15,000 ppm,including 500 to 10,000 ppm, for example 1000 to 5,000 ppm. In brineswhere both Ca²⁺ and Mg²⁺ are present, the molar ratio of Ca²⁺ to Mg²⁺(i.e., Ca²⁺:Mg²⁺) in the subterranean brine may vary, and in oneembodiment may range between 1:1 and 100:1. In some instance theCa²⁺:Mg²⁺ may be between 1:1 and 1:2.5; 1:2.5 and 1:5; 1:5 and 1:10;1:10 and 1:25; 1:25 and 1:50; 1:50 and 1:100; 1:100 and 1:150; 1:150 and1:200; 1:200 and 1:250; 1:250 and 1:500; 1:500 and 1:1000, or a rangethereof. For example, the molar ratio of Ca²⁺ to Mg²⁺ in subterraneanbrines of interest may range between 1:1 and 1:10; 1:5 and 1:25; 1:10and 1:50; 1:25 and 1:100; 1:50 and 1:500; or 1:100 and 1:1000. In someembodiments, the ratio of Mg²⁺ to Ca²⁺ (i.e., Mg²⁺:Ca²⁺) in thesubterranean brine ranges between 1:1 and 1:2.5; 1:2.5 and 1:5; 1:5 and1:10; 1:10 and 1:25; 1:25 and 1:50; 1:50 and 1:100; 1:100 and 1:150;1:150 and 1:200; 1:200 and 1:250; 1:250 and 1:500; 1:500 and 1:1000, ora range thereof. For example, the ratio of Mg²⁺ to Ca²⁺ in thesubterranean brines of interest may range between 1:1 and 1:10; 1:5 and1:25; 1:10 and 1:50; 1:25 and 1:100; 1:50 and 1:500; or 1:100 and1:1000. In particular embodiments the Mg²⁺:Ca²⁺ of a brine may be lowerthan 1:1, such as 1:2, 1:4, 1:10, 1:100 or lower.

In some embodiments, subterranean brines provide a source of alkalinityand contain proton-removing agents. As used herein, “proton removingagent” includes a substance or compound which possesses sufficientalkalinity or basicity to remove one or more protons from aproton-containing species in solution. In some embodiments, the amountof proton-removing agent is an amount such that the subterranean brinepossesses a neutral pH (i.e., pH=7). In these embodiments, thestoichiometric sum of proton-removing agents is equal to thestoichiometric sum of proton-containing agents in the subterraneanbrine. The stoichiometric sum of proton-removing agents is the sum ofall substances or compounds (e.g., halides, oxyanions, organic bases,etc.) which can remove one or more protons from a proton-containingspecies in solution. In other embodiments, the amount of proton-removingagents in the subterranean brine is an amount such that the subterraneanbrine is alkaline. In some instances, the alkaline subterranean brinehas a pH that is above neutral pH (i.e., pH>7), e.g., the brine has a pHranging from 7.1 to 12, such as 8 to 12, such as 8 to 11, and including9 to 11. Proton-removing agents present in subterranean brines of theinvention may vary. In some embodiments, the proton-removing agents maybe anions. Anions may be halides, such as Cl⁻, F⁻, I⁻ and Br⁻, amongothers and oxyanions, e.g., sulfate, carbonate, borate and nitrate,among others.

In some embodiments, the proton-removing agent is borate. Boratespresent in subterranean brines of the invention may be any oxyanion ofboron, e.g., BO₃ ³⁻, B₂O₅ ⁴⁻, B₃O₇ ⁵⁻, and B₄O₉ ⁶⁻, among others. Theamount of borate present in subterranean brines of the invention mayvary. In some instances, the amount of borate present ranges from 50 to100,000 ppm, such as 100 to 75,000 ppm, including 500 to 50,000 ppm, forexample 1000 to 25,000 ppm. As such, in some embodiments, the protonremoving agents present in the subterranean brines may comprise 5% ormore of borates, such about 10% or more of borates, including about 25%or more of borates, for instance about 50% or more of borates, such asabout 75% or more of borates, including about 90% or more of borates.Where both carbonate and borate are present, the molar ratio ofcarbonate to borate (i.e., carbonate:borate) in the subterranean brinesmay be between 1:1 and 1:2.5; 1:2.5 and 1:5; 1:5 and 1:10; 1:10 and1:25; 1:25 and 1:50; 1:50 and 1:100; 1:100 and 1:150; 1:150 and 1:200;1:200 and 1:250; 1:250 and 1:500; 1:500 and 1:1000, or a range thereof.For example, the molar ratio of carbonate to borate in subterraneanbrines of the invention may be between 1:1 and 1:10; 1:5 and 1:25; 1:10and 1:50; 1:25 and 1:100; 1:50 and 1:500; or 1:100 and 1:1000. In otherembodiments, the ratio of carbonate to borate (i.e., carbonate:borate)in the subterranean brine may be between 1:1 and 2.5:1; 2.5:1 and 5:1;5:1 and 10:1; 10:1 and 25:1; 25:1 and 50:1; 50:1 and 100:1; 100:1 and150:1; 150:1 and 200:1; 200:1 and 250:1; 250:1 and 500:1; 500:1 and1000:1, or a range thereof. For example, the ratio of carbonate toborate in the subterranean brines of the invention may be between 1:1and 10:1; 5:1 and 25:1; 10:1 and 50:1; 25:1 and 100:1; 50:1 and 500:1;or 100:1 and 1000:1.

In some embodiments, proton-removing agents present in subterraneanbrines may be an organic base. In some instances, the organic base maybe a monocarboxylic acid anion, e.g., formate, acetate, propionate,butyrate, and valerate, among others. In other instances, the organicbase may be a dicarboxylic acid anion, e.g., oxalate, malonate,succinate, and glutarate, among others. In other instances, the organicbase may be phenolic compounds, e.g., phenol, methylphenol, ethylphenol,and dimethylphenol, among others. In some embodiments, the organic basemay be a nitrogenous base, e.g., primary amines such as methyl amine,secondary amines such as diisopropylamine, tertiary amines such asdiisopropylethylamine, aromatic amines such as aniline, heteroaromaticssuch as pyridine, imidazole, and benzimidazole, and various formsthereof. The amount of organic base present in subterranean brines ofthe invention may vary. In some instances, the amount of organic basepresent in the brine ranges from 1 to 200 mmol/liter, such as 1 to 175mmol/liter, such as 1 to 100 mmol/liter, such as 10 to 100 mmol/liter,including 10 to 75 mmol/liter. Thus, in certain embodiments, protonremoving agents present in the subterranean brines may make up 5% ormore of organic base, such about 10% or more of organic base, includingabout 25% or more of organic base, for instance about 50% or more oforganic base, such as about 75% or more of organic base, including about90% or more of organic base.

In some embodiments, subterranean brines of the invention may have acomposition which includes one or more identifying components whichdistinguish each subterranean brine from other subterranean brines. Assuch, the composition of each subterranean brine may be distinct fromone another. In some embodiments, subterranean brines may bedistinguished from one another by the amount and type of elements, ionsor other substances present in the subterranean brine (e.g., trace metalions, Hg, Se, As, etc). In other embodiments, subterranean brines may bedistinguished from one another by the molar ratio of carbonates presentin the subterranean brine. In other embodiments, subterranean brines maybe distinguished from one another by the amount and type of differentisotopes present in the subterranean brine (e.g., δ¹³C, δ¹⁸O, etc.). Inother embodiments, subterranean brines may be distinguished from oneanother by the isotopic ratio of particular elements present in thesubterranean brine (e.g., ⁸⁷Sr/⁸⁶Sr).

Methods

A variety of different methods may be employed to prepare the CO₂sequestering calcium carbonates of the compositions provided herein. TheCO₂ sequestration protocols of interest include, but are not limited to,those disclosed in U.S. Pat. Nos. 7,735,274, 7,744,761, 7,754,169, and7,749,476; and U.S. patent application Ser. No. 12/557,492, titled “CO₂COMMODITY TRADING SYSTEM AND METHOD,” filed 10 Sep. 2009; InternationalApplication No. PCT/US08/88318, titled, “METHODS OF SEQUESTERING CO₂,”filed 24 Dec. 2008; and International Application No. PCT/US09/45722,titled “ROCK AND AGGREGATE, AND METHODS OF MAKING AND USING THE SAME,”filed 29 May 2009; as well as U.S. Provisional Patent Application Ser.Nos. 61/081,299; 61/082,766; 61/088,347; 61/088,340; and 61/101,631; thedisclosures of which are herein incorporated by reference in theirentireties.

FIG. 2 provides an illustrative schematic flow diagram of a carbonateprecipitation process according to some embodiments of the invention. InFIG. 2, any source of water, such as, for example only, saltwater fromsalt water source containing alkaline earth metal ions or an alkalineearth metal ion containing water 10 is subjected to one or moreconditions at precipitation step 20. In some embodiments, the water fromsaltwater source or the alkaline earth-metal containing water 10 iscontacted with a solution charged with the partially or fully dissolvedCO₂, which CO₂ is then subjected to one or more carbonate compoundprecipitation conditions. As depicted in FIG. 2, the CO₂ 30 includes agaseous stream or the solution containing the CO₂ where the CO₂ has beencontacted with the proton removing agent.

In some embodiments, the solution charged with the partially or fullydissolved CO₂ is made by parging or diffusing the CO₂ gaseous streamthrough a solution to make a CO₂ charged water. In some embodiments, thesolution with CO₂ includes a proton removing agent. In some embodiments,the CO₂ gas is bubbled or parged through a solution containing a protonremoving agent, such as sodium or potassium hydroxide, in an absorber.In some embodiments, the absorber may include a bubble chamber where theCO₂ gas is bubbled through the solution containing the proton removingagent. In some embodiments, the absorber may include a spray tower wherethe solution containing the proton removing agent is sprayed orcirculated through the CO₂ gas. In some embodiments, the absorber mayinclude a pack bed to increase the surface area of contact between theCO₂ gas and the solution containing the proton removing agent. In someembodiments, a typical absorber fluid temperature is 32-37° C. Theabsorber for absorbing CO₂ in the solution is described in U.S.application Ser. No. 12/721,549, filed on Mar. 10, 2010, which isincorporated herein by reference in its entirety.

In some embodiments, the water from saltwater source or an alkalineearth-metal containing water 10 is contacted with a gaseous stream ofCO₂ or the CO₂ charged water from the source of CO₂ 30. By CO₂ chargedwater is meant water that has had CO₂ gas contacted with it and/or whereCO₂ molecules have combined with water molecules to produce, e.g.,carbonic acid, bicarbonate and carbonate ion. Charging water in thisstep results in an increase in the CO₂ content of the water, e.g., inthe form of carbonic acid, bicarbonate and carbonate ion, and aconcomitant decrease in the pCO₂ of the waste stream that is contactedwith the water. The CO₂ charged water may be acidic, having a pH of 6 orless, such as 5 or less and including 4 or less. In certain embodiments,the concentration of CO₂ gas that is used to charge the water is 10% orhigher, 25% or higher, including 50% or higher, such as 75% or evenhigher.

In some embodiments, an order for the addition of the CO₂ and thealkaline earth metal containing water to the reactor for theprecipitation, may be varied. In some embodiments, the CO₂ gaseousstream or the solution containing the partially or fully dissolved CO₂or the affluent from the absorber containing an alkaline solution of CO₂is added to the reactor containing the alkaline earth-metal containingwater for precipitation of the carbonate precipitate in theprecipitation step 20. In some embodiments, the alkaline earth-metalcontaining water is added to the reactor containing the CO₂ gaseousstream or the solution containing the partially or fully dissolved CO₂or the affluent from the absorber containing an alkaline solution of CO₂for precipitation of the carbonate precipitate in the precipitation step20. In some embodiments, the alkaline earth-metal containing water isadded to the reactor containing less than 20%, or less than 15%, or lessthan 10%, or less than 5% of the CO₂ gaseous stream or the solutioncontaining the partially or fully dissolved CO₂ or the affluent from theabsorber containing an alkaline solution of CO₂ for precipitation of thecarbonate precipitate in the precipitation step 20.

As shown in FIG. 2, in some embodiments, the stabilizer is added to thesolution containing CO₂ or CO₂ charged water 30 which is then contactedwith the alkaline earth metal ions in the precipitation step 20. In someembodiments, the stabilizer is added to the alkaline earth metal ions 10which is then contacted with the solution containing CO₂ in theprecipitation step 20. In such embodiments, the stabilizer may bedissolved in the alkaline earth metal containing solution before it isadded to the solution containing CO₂. In some embodiments, thestabilizer is added to the precipitation step 20 in the reactor beforeboth the alkaline earth metal ions and the solution of CO₂ are added. Insome embodiments, the stabilizer is added to the precipitation step 20simultaneously when both the alkaline earth metal ions and the solutionof CO₂ are added for the precipitation. In some embodiments, thestabilizer is added to the precipitation step 20 after both the alkalineearth metal ions and the solution of CO₂ are added for theprecipitation. In some embodiments, the stabilizer is added to theslurry containing the carbonate precipitate that is taken out from theprecipitation step 20.

By way of example only, in some embodiments, about 1-50 lbs of sodiumsulfate salt may be added to about 100-200 gallons of water in a tank,and may be dissolved by mixing with both impeller and recirculationpumps. This solution may be transferred to a larger tank, containing anadditional about 2000-4000 gallons of water, which may be mixed byrecirculation pumps. About 200-400 gallons of concentrated calciumchloride solution may be added to this tank. The solution may be mixedby recirculation for 1-4 hours. Additional sodium sulfate salt, calciumchloride concentrate and/or water may be added to perform fineadjustments to concentrations. This resulting solution is then mixedwith CO₂ charged water to form the precipitate.

Contact protocols include, but are not limited to, direct contactingprotocols, e.g., bubbling the gas through the volume of water;concurrent contacting means, e.g., contact between unidirectionallyflowing gaseous and liquid phase streams; and countercurrent means,e.g., contact between oppositely flowing gaseous and liquid phasestreams, and the like. Thus, contact may be accomplished through use ofinfusers, bubblers, fluidic Venturi reactor, sparger, gas filter, spray,tray, or packed column reactors, and the like, as may be convenient. Insome embodiments, the contact is by spray. In some embodiments, thecontact is through packed column.

In some embodiments, the methods include contacting the volume of waterthat is subjected to the mineral precipitation conditions with a sourceof CO₂. The contacting of the water with the source of CO₂ may occurbefore and/or during the time when the water is subject to CO₂ in one ormore conditions or one or more precipitation conditions. Accordingly,embodiments of the invention include methods in which the volume ofwater is contacted with a source of CO₂ prior to subjecting the volumeof saltwater to mineral precipitation conditions. Embodiments of theinvention include methods in which the volume of salt water is contactedwith a source of CO₂ while the volume of saltwater is being subjected tomineral precipitation conditions. Embodiments of the invention includemethods in which the volume of water is contacted with a source of a CO₂both prior to subjecting the volume of water to mineral precipitationconditions and while the volume of water is being subjected to carbonatecompound precipitation conditions. In some embodiments, the same watermay be cycled more than once, wherein a first cycle of precipitationremoves primarily calcium carbonate and magnesium carbonate minerals,and leaves remaining alkaline water to which other alkaline earth ionsources may be added, that can have more carbon dioxide or the solutionof carbon dioxide cycled through it, precipitating more carbonatecompounds.

The CO₂ charging and carbonate compound precipitation may occur in acontinuous process or at separate steps. As such, charging andprecipitation may occur in the same reactor of a system, e.g., asillustrated in FIG. 2 at step 20, according to some embodiments of theinvention. In yet other embodiments, these two steps may occur inseparate reactors, such that the water containing proton removing agentis first charged with CO₂ in a charging reactor and the resultant CO₂charged water or the solution is then subjected to precipitationconditions in a separate reactor or in a precipitator.

In methods provided herein, a volume of water is subjected to one ormore conditions or precipitation conditions sufficient to produce aprecipitated carbonate compound composition and mother liquor (i.e., thepart of the water that is left over after precipitation of the carbonatecompound(s) from water). At precipitation step 20, carbonate compounds,which may be amorphous or crystalline, are precipitated. Thisprecipitate may be the self-cementing composition product 80 and may bestored as is or may be further processed to make the cement products.Alternatively, the precipitate may be subjected to further processing togive the hydraulic cement or the SCM compositions of the invention.

The one or more conditions or one or more precipitation conditions ofinterest include those that change the physical environment of the waterto produce the desired precipitate product. The one or more conditionsor precipitation conditions include, but are not limited to, one or moreof temperature, pressure, pH, precipitation, residence time of theprecipitate, flow rate of the solutions, concentration, dewatering orseparation of the precipitate, drying, milling, and storage. Forexample, the temperature of the water may be within a suitable range forthe precipitation of the desired composition to occur. For example, thetemperature of the water may be raised to an amount suitable forprecipitation of the desired carbonate compound(s) to occur. In suchembodiments, the temperature of the water may be from 5 to 70° C., suchas from 20 to 50° C., and including from 25 to 45° C. As such, while agiven set of precipitation conditions may have a temperature rangingfrom 0 to 100° C., the temperature may be raised in certain embodimentsto produce the desired precipitate. In certain embodiments, thetemperature is raised using energy generated from low or zero carbondioxide emission sources, e.g., solar energy source, wind energy source,hydroelectric energy source, etc.

The residence time of the precipitate in the reactor before theprecipitate is removed from the solution, may vary. In some embodiments,the residence time of the precipitate in the solution is more than 5seconds, or between 5 seconds-1 hour, or between 5 seconds-1 minute, orbetween 5 seconds to 20 seconds, or between 5 seconds to 30 seconds, orbetween 5 seconds to 40 seconds. Without being limited by any theory, itis contemplated that the residence time of the precipitate may affectthe size of the particle. For example, a shorter residence time may givesmaller size particles or more disperse particles whereas longerresidence time may give agglomerated or larger size particles. In someembodiments, the residence time in the process of the invention may beused to make small size as well as large size particles in a single ormultiple batches which may be separated or may remain mixed for latersteps of the process. In some embodiments, the finely disperse particlesmay be processed further to give the SCM composition of the invention.In some embodiments, the large or agglomerated particles may beprocessed to give the hydraulic cement composition and/or theself-cementing composition of the invention. The particle size and/oragglomeration of the particles may also be affected by the stabilizeradded during the precipitation reaction or shortly thereafter.

While the pH of the water may range from 7 to 14 during a givenprecipitation process, in some embodiments, the pH is raised to alkalinelevels in order to drive the precipitation of carbonate compound asdesired. In some embodiments, the pH is raised to a level whichminimizes if not eliminates CO₂ gas generation production duringprecipitation. In these embodiments, the pH may be raised to 10 orhigher, such as 11 or higher. In some embodiments, the one or moreconditions or the precipitation conditions include contacting the protonremoving agent with CO₂ to form a solution which is then contacted withthe solution containing alkaline earth metal ions. In some embodiments,the one or more conditions or the precipitation conditions includecontacting the saltwater or the alkaline-earth metal containing waterwith a proton removing agent. The proton removing agent may be anyproton removing agent, as described herein, for example, but not limitedto, oxide, hydroxide, such as sodium hydroxide, carbonate, coal ash,naturally occurring mineral, and combination thereof. In someembodiments, the one or more conditions or the precipitation conditionsinclude contacting the saltwater or the alkaline-earth metal containingwater to electrochemical conditions. Such electrochemical conditionshave been described herein. The nature of the precipitate may beaffected by the pH of the precipitation process. In some embodiments,high pH may lead to rapid precipitation and agglomeration of theparticles whereas lower pH or slow raise in the pH may lead to finerparticles.

The nature of the precipitate may also be influenced by selection ofappropriate major ion ratios. Major ion ratios may have influence onpolymorph formation. For example, magnesium may stabilize the vateriteand/or amorphous calcium carbonate in the precipitate.

Rate of precipitation may also influence compound polymorphic phaseformation and may be controlled in a manner sufficient to produce adesired precipitate product. The most rapid precipitation can beachieved by seeding the solution with a desired phase. Without seeding,rapid precipitation can be achieved by rapidly increasing the pH of thesea water. The higher the pH is, the more rapid the precipitation maybe.

In some embodiments, a set of conditions to produce the desiredprecipitate from the water include, but not limited to, the water'stemperature and pH, and in some instances the concentrations ofadditives and ionic species in the water. Precipitation conditions mayalso include factors such as mixing rate, forms of agitation such asultrasonics, and the presence of seed crystals, catalysts, membranes, orsubstrates. In some embodiments, precipitation conditions includesupersaturated conditions, temperature, pH, and/or concentrationgradients, or cycling or changing any of these parameters. The protocolsemployed to prepare carbonate compound precipitates according to theinvention may be batch or continuous protocols. It will be appreciatedthat precipitation conditions may be different to produce a givenprecipitate in a continuous flow system compared to a batch system. Theone or more of the precipitation conditions, as described herein, may bemodulated to obtain a precipitate with a desired particle size,reactivity, and zeta potential. This may further affect the compressivestrength of the cement formed when the composition is combined withfresh water, set and hardenend.

Following production of the carbonate compound precipitate from thewater, the resultant precipitated carbonate compound composition may beseparated from the mother liquor or dewatered to produce the precipitateproduct, as illustrated at step 40 of FIG. 1. Alternatively, theprecipitate is left as is in the mother liquor or mother suprenate. Theprecipitate contains vaterite and the stabilizer.

Separation of the precipitate can be achieved using any convenientapproach, including a mechanical approach, e.g., where bulk excess wateris drained from the precipitated, e.g., either by gravity alone or withthe addition of vacuum, mechanical pressing, by filtering theprecipitate from the mother liquor to produce a filtrate, or usingcentrifugation techniques, etc. Separation of bulk water produces a wet,dewatered precipitate.

The above protocol results in the production of slurry of a CO₂sequestering precipitate and mother liquor. This precipitate in themother liquor and/or in the slurry may give the self-cementingcomposition 80. In some embodiments, a portion or whole of the dewateredprecipitate or the slurry is further prcessed to make the hydrauliccement or the SCM compositions of the invention.

Where desired, the compositions made up of the precipitate and themother liquor may be stored for a period of time following precipitationand prior to further processing. For example, the composition may bestored for a period of time ranging from 1 to 1000 days or longer, suchas 1 to 10 days or longer, at a temperature ranging from 1 to 40° C.,such as 20 to 25° C.

The slurry components are then separated. Embodiments may includetreatment of the mother liquor, where the mother liquor may or may notbe present in the same composition as the product. For example, wherethe mother liquor is to be returned to the ocean, the mother liquor maybe contacted with a gaseous source of CO₂ in a manner sufficient toincrease the concentration of carbonate ion present in the motherliquor. Contact may be conducted using any convenient protocol, such asthose described above. In certain embodiments, the mother liquor has analkaline pH, and contact with the CO₂ source is carried out in a mannersufficient to reduce the pH to a range between 5 and 9, e.g., 6 and 8.5,including 7.5 to 8.2. In certain embodiments, the treated brine may becontacted with a source of CO₂, e.g., as described above, to sequesterfurther CO₂.

The resultant mother liquor of the reaction may be disposed of using anyconvenient protocol. In certain embodiments, it may be sent to atailings pond for disposal 42. In certain embodiments, it may bedisposed of in a naturally occurring body of water, e.g., ocean, sea,lake or river. In certain embodiments, the mother liquor is returned tothe source of feedwater for the methods of invention, e.g., an ocean orsea. Alternatively, the mother liquor may be further processed, e.g.,subjected to desalination protocols, as described further in U.S. Pat.No. 7,744,761, the disclosure of which is herein incorporated byreference in its entirety.

In some embodiments, the stability of the vaterite in the precipitatecan be optionally optimized by rinsing the precipitate with chemicalactivators. In one aspect, there are provided methods for making acomposition, comprising (a) contacting CO₂ from a CO₂ source with aproton removing agent to form a solution; (b) contacting the solutionwith water comprising alkaline earth-metal and a stabilizer under one ormore conditions to make a precipiate comprising vaterite and thestabilizer; and (c) rinsing the precipitate with solution comprisingchemical activators that activate the vaterite in the precipitate. Insome embodiments, the method further comprises drying the precipitate toform the composition of the invention. In some embodiments, the methodfurther comprises combining the composition with water and facilitatingvaterite transformation to aragonite when the composition sets andhardens to form cement wherein the facilitation is provided by thechemical activators.

In some embodiments of the above described aspect, the stability of theprecipitate containing vaterite and stabilizer may be further optimizedby rinsing the precipitate with chemical additives or activators. Forexample, in some embodiments, it may be desired to stabilize thevaterite precipitate only during the precipitation process. In suchembodiments, the stabilizer may be added during the precipitationprocess and is partially or fully removed after the precipitation byrinsing the precipitate with solution containing chemical activators. Insome embodiments, the precipitate may have been obtained by separatingthe solid from the slurry and filter pressing the settled solid. Suchrinsing may remove the stabilizer from the precipitate therebyactivating the vaterite or making the vaterite less stable and morereactive. In some embodiments, it may be desired to stabilize thevaterite precipitate not only during the precipitation process but alsoduring the drying process (as described herein). In such embodiments,the dried composition may be kept in storage and is rinsed with chemicalactivators at the time of use to generate a reactive vaterite. In someembodiments, the vaterite precipitate may get over stabilized by thestabilizer and it may be desired to destabilize the vateriteprecipitate. In such embodiments, the precipitate or the driedcomposition is rinsed with chemical activators to generate a reactive ordestabilized vaterite. As described herein, the stability of thevaterite is related to the optimized activation of the vaterite suchthat when the composition is combined with water, the vateritetransforms to aragonite resulting in cementation.

In some embodiments, the chemical activators are solutions comprisingcarbonate ions and/or magnesium ions. In such embodiments, the abovedescribed rinsing comprises rinsing the precipitate or the driedcomposition with a first solution comprising carbonate ions and then asecond solution comprising magnesium ions. In some embodiments, theprecipitate or the dried composition may be rinsed with a solutioncomprising magnesium carbonate such that the solution provides both themagnesium ions as well as carbonate ions. It is contemplated that therinsing with the first solution comprising carbonate ions modifies thesurface chemistry of the precipitate in such a way that the sulfate ionsin the precipitate are partially or fully replaced by the carbonate ionsmaking the overall surface charge negative. It is further contemplatedthat the rinsing with the second solution comprising magnesium ionspartially or fully replaces the carbonate ions with the magnesium ionssuch that the overall surface charge is positive. The reduction in thesulfate content of the precipitate and subsequent rinsing with magnesiumions may activate vaterite and facilitate transformation of vaterite toaragonite when the composition is combined with water. The examples ofsuch rinsing are described herein in Example 9.

The resultant dewatered precipitate is then dried to produce thecomposition of the invention, as illustrated at step 60 of FIG. 1.Drying can be achieved by air drying, spray drying, vacuum drying,and/or oven drying the precipitate. Where the precipitate is air dried,air drying may be at a temperature ranging from −70 to 120° C., asdesired. In certain embodiments, drying is achieved by freeze-drying(i.e., lyophilization), where the precipitate is frozen, the surroundingpressure is reduced and enough heat is added to allow the frozen waterin the material to sublime directly from the frozen precipitate phase togas. In yet another embodiment, the precipitate is spray dried to drythe precipitate, where the liquid containing the precipitate is dried byfeeding it through a hot gas (such as the gaseous waste stream from thepower plant), e.g., where the liquid feed is pumped through an atomizerinto a main drying chamber and a hot gas is passed as a co-current orcounter-current to the atomizer direction. Depending on the particulardrying protocol of the system, the drying station may include afiltration element, freeze drying structure, spray drying structure,etc. The drying of the precipitate may include temperature between150-180° C. or between 150-250° C., or between 150-200° C. Thedischarged air may include finer particles 62.

In some embodiments, the step of spray drying may include separation ofdifferent sized particles of the precipitate. For example, a first batchof larger sized particles may be collected from the spray dryer followedby the collection of the smaller sized particles. In some embodiments, asingle batch may give one or more, such as, for example only, two,three, four, or five different sizes of the particles (e.g., micron andsub-micron particles as defined herein) which may be separated for lateruse or which different sized particle may be mixed together to make thecomposition of the invention.

In some embodiments, the particles with different morphologies, such asfine or agglomerated, and/or the particles with different sizes may bemixed to make the compositions of the invention. For example, acomposition of the invention may include a mix of fine disperseparticles with larger agglomerated particles or the composition of theinvention may include a mix of particles with different sizes, e.g.,particles with sizes ranging between 0.1 micron to 100 micron. In someembodiments, the composition of the invention may be modulated by mixingthe particles with different particle size, surface area, zetapotential, and/or morphologies.

Where desired, the dewatered precipitate product from the separationreactor 40 may be washed before drying, as illustrated at step 50 ofFIG. 1. The precipitate may be washed with freshwater, e.g., to removesalts (such as NaCl) from the dewatered precipitate. The water used forwashing may contain metals, such as, iron, nickel, etc. In someembodiments, the precipitate may be rinsed with fresh water to removehalite or the chloride content from the precipitate. The chloride may beundesirable in some applications, for example, in aggregates intendedfor use in concrete since the chloride has a tendency to corrode rebar.In some embodiments, the precipitate may be washed with a solutionhaving a low chloride concentration but high concentration of divalentcations (such as, calcium, magnesium, etc.). The stabilization of themetastable carbonate forms in the precipitate due to the presence of thestabilizer may prevent the dissolution of the precipitate, therebyreducing the yield loss and the conversion to cemented material. Usedwash water may be disposed of as convenient, e.g., by disposing of it ina tailings pond, etc.

At step 70, the dried precipitate is the vaterite containingcomposition. The vaterite containing composition may be optionallyactivated by refining, milling, aging, and/or curing, e.g., to providefor desired physical characteristics, such as activation, particle size,surface area, zeta potential, etc. The vaterite containing compositionmay also be activated by adding an aragonite seed, inorganic additive ororganic additive, as described herein. Further, one or more componentsmay be added to the composition, such as admixtures, aggregate,supplementary cementitious materials, etc., to produce a finalcomposition of the invention 80. Refinement may include a variety ofdifferent protocols. In certain embodiments, the product is subjected tomechanical refinement, e.g., grinding, in order to obtain a product withdesired physical properties, e.g., particle size, etc. The driedprecipitate may be milled or ground to obtain a desired particle size.

Systems

Aspects and embodiments provided herein further include systems, e.g.,processing plants or factories, for producing the carbonate compoundcompositions, e.g., saltwater derived carbonate and hydroxide mineralcompositions, and cements, as well as concretes and mortars that includethe cements provided herein. Systems provided herein may have anyconfiguration which enables practice of the particular production methodof interest.

In one aspect, there is provided a system for making the composition ofthe invention, including (a) an input for an alkaline earth-metalcontaining water; (b) an input for a flue gas from an industrial plantincluding carbon of a fossil fuel origin; (c) an input for a stabilizer;and (d) a reactor connected to the inputs of (a), (b), and (c) that isconfigured to make the composition of the invention. In another aspect,there is provided a system for making a composition, including (a) aninput for an alkaline earth-metal containing water; (b) an input for aCO₂ source; (c) an input for a stabilizer; and (d) a reactor connectedto the inputs of (a), (b), and (c) that is configured to make acomposition. The composition in such embodiments includes metastablecarbonate and a stabilizer.

In another aspect, there are provided systems for making the compositionof the invention, including (a) an input for an alkaline earth-metalcontaining water; (b) an input for a flue gas from an industrial plantincluding carbon of a fossil fuel origin; (c) an input for a stabilizer;(d) a reactor connected to the inputs of (a), (b), and (c) that isconfigured to make the composition comprising vaterite; and (e) anactivation station to activate vaterite containing composition. Inanother aspect, there is provided a system for making a composition,including (a) an input for an alkaline earth-metal containing water; (b)an input for a CO₂ source; (c) an input for a stabilizer; (d) a reactorconnected to the inputs of (a), (b), and (c) that is configured to makethe composition; and (e) an activation station to activate vateritecontaining composition.

FIG. 3 provides an illustrative schematic of a system to conduct themethods of some embodiments of the invention. In FIG. 3, system 100includes water source 110, such as, alkaline earth-metal containingwater. In some embodiments, water source 110 includes a structure havingan input for salt water, such as a pipe or conduit from an ocean, etc.Where the salt water source is seawater, the input is in fluidcommunication with a source of sea water. For example, the input is apipe line or feed from ocean water to a land based system or an inletport in the hull of ship, e.g., where the system is part of a ship,e.g., in an ocean based system. Water may be removed and sent to thesystems provided herein by any convenient protocol, such as, but notlimited to, turbine motor pump, rotary lobe pump, hydraulic pump, fluidtransfer pump, geothermal well pump, a water-submersible vacuum pump,among other protocols.

The methods and systems provided herein may also include one or moredetectors configured for monitoring the source of water or the source ofcarbon dioxide (not illustrated in FIG. 1 or FIG. 2). Monitoring mayinclude, but is not limited to, collecting data about the pressure,temperature and composition of the water or the carbon dioxide gas. Thedetectors may be any convenient device configured to monitor, forexample, pressure sensors (e.g., electromagnetic pressure sensors,potentiometric pressure sensors, etc.), temperature sensors (resistancetemperature detectors, thermocouples, gas thermometers, thermistors,pyrometers, infrared radiation sensors, etc.), volume sensors (e.g.,geophysical diffraction tomography, X-ray tomography, hydroacousticsurveyers, etc.), and devices for determining chemical makeup of thewater or the carbon dioxide gas (e.g, IR spectrometer, NMR spectrometer,UV-vis spectrophotometer, high performance liquid chromatographs,inductively coupled plasma emission spectrometers, inductively coupledplasma mass spectrometers, ion chromatographs, X-ray diffractometers,gas chromatographs, gas chromatography-mass spectrometers,flow-injection analysis, scintillation counters, acidimetric titration,and flame emission spectrometers, etc.).

In some embodiments, detectors for monitoring the subterranean brine mayalso include a computer interface which is configured to provide a userwith the collected data about the water or the carbon dioxide gas. Forexample, a detector may determine the internal pressure of the water orthe carbon dioxide gas and the computer interface may provide a summaryof the changes in the internal pressure within the water or the carbondioxide gas over time. In some embodiments, the summary may be stored asa computer readable data file or may be printed out as a user readabledocument.

In some embodiments, the detector may be a monitoring device such thatit can collect real-time data (e.g., internal pressure, temperature,etc.) about the water or the carbon dioxide gas. In other embodiments,the detector may be one or more detectors configured to determine theparameters of the water or the carbon dioxide gas at regular intervals,e.g., determining the composition every 1 minute, every 5 minutes, every10 minutes, every 30 minutes, every 60 minutes, every 100 minutes, every200 minutes, every 500 minutes, or some other interval.

FIG. 3 also shows a stabilizer source 110′. This source may vary, asdescribed above. In some embodiments, the stabilizer source 110′includes a structure having an input for the stabilizer, such as a pipeor conduit. FIG. 3 also shows a CO₂ source 130. This source may vary, asdescribed above. In some embodiments, the CO₂ source 130 includes astructure having an input for CO₂, such as a pipe or conduit. Where theCO₂ source is flue gas from the power plant, the input is in gaseouscommunication with the source of CO₂ in the plant. For example, theinput is a pipe line or feed from power plant to the system.Alternatively, the CO₂ source may be a cylinder or series of cylindersconnected to the input for the CO₂ source. In some embodiments, the CO₂source is a solution containing CO₂ obtained after contacting CO₂ from asource of CO₂ with a solution containing proton removing agent.

The inputs for the water source, alkaline earth metal ion source, thestabilizer source and the CO₂ source are connected to the CO₂ chargerand precipitator reactor 120. The precipitation reactor 120 is connectedto the inputs and is configured to make the carbonate precipitate. Thecharger and precipitation reactor 120 may be configured to include anynumber of different elements, such as temperature regulators (e.g.,configured to heat the water to a desired temperature), chemicaladditive elements, e.g., for introducing chemical pH elevating agents(such as NaOH) into the water, electrolysis elements, e.g.,cathodes/anodes, etc. This reactor 120 may operate as a batch process ora continuous process. It is to be understood that system in FIG. 3 isfor illustration purposes only and that the system may be modified toachieve the same result. For example, the system may have more than onereactor, and/or more than one source of alkaline earth metal ions,and/or more than one source of stabilizer; and/or more than one sourceof CO₂ interconnected in the system. The charger and/or reactor can be acontinuous stir tank reactor (CSTR), plug flow reactor (PFR), a tank, abatch reactor, or combination thereof. Such reactors, such as, CSTR,PFR, etc. are well known in the art. In some embodiments, the reactor isPFR. The PFR may have pipes optionally with inline mixing elements tomix the solutions. In some embodiments, the turbulence in the pipe mixesthe solutions without the need for mixing elements. In some embodiments,static inline mixing elements may be present inside the pipes to mix thesolutions. The length and the diameter of the pipes may be modulatedthat may affect the mixing of the solutions, the residence time of theprecipitate, the morphology of the precipitate, the particle size of theprecipitate, etc. In some embodiments, the inside of the pipes in thePFR may be coated with a material that resists the build up of theprecipitate inside the pipes. Such coating can be Teflon or any othermaterial. An average flow of the solution containing the partially orfully dissolved CO₂ or the affluent from the absorber containing analkaline solution of CO₂ to the reactor may be 4-6 GPM (gallons perminute), or 5-6 GPM, or 4-5 GPM, or 3-8 GPM. An average flow of thealkaline earth metal ion containing water to the reactor may be 8-10 GPM(gallons per minute), or 8-9 GPM, or 9-10 GPM, or 5-15 GPM.

The product of the precipitation reaction, e.g., the slurry may beremoved from the reactor and used to make the self-cementing productdescribed herein. Alternatively, the product of the precipitationreaction, e.g., the slurry is then processed at a bulk dewateringstation 140, as illustrated in FIG. 3. The dewatering station 140 mayuse a variety of different water removal processes, including processessuch as continuous centrifugation, centrifugation, filtercentrifugation, gravitational settling, and the like. The slurryobtained after bulk dewatering but still wetted in a mother supernatecan be used to make the self-cementing composition provided herein. Thedewatering station 140 may be any number of dewatering stationsconnected to each other to dewater the slurry (e.g., parallel, inseries, or combination thereof).

In some embodiments, systems may also include a desalination station(not illustrated in FIG. 3). The desalination station may be in fluidcommunication with the liquid-solid separator 140 such that the liquidproduct may be conveyed from the liquid-solid separator to thedesalination station directly. The systems may include a conveyance(e.g., pipe) where the output depleted brine may be directly pumped intothe desalination station or may flow to desalination station by gravity.Desalination stations of the invention may employ any convenientprotocol for desalination, and may include, but are not limited todistillers, vapor compressors, filtration devices, electrodialyzers,ion-exchange membranes, nano-filtration membranes, reverse osmosisdesalination membranes, multiple effect evaporators or a combinationthereof.

The system shown in FIG. 3 may also include a drying station 160 or aseries of drying stations for drying the dewatered precipitate producedat station 140. Depending on the particular drying protocol of thesystem, the drying station 160 may include a filtration element, freezedrying structure, oven drying, spray drying structure, etc., asdescribed above.

Also shown in FIG. 3, is an optional washing station 150, where bulkdewatered precipitate from separation station 140 is washed, e.g., toremove salts and other solutes from the precipitate, prior to drying atthe drying station 160. Dried precipitate from station 160 is then sentto activation station 170, where the precipitate may be mechanicallyprocessed and/or one or more components may be added to the precipitate(e.g., as described above) to produce the compositions containingvaterite, as provided herein. The activation station 170 may havegrinders, millers, crushers, compressors, blender, etc. in order toobtain desired physical properties in the composition of the invention.

The system may further include outlet conveyers, e.g., conveyer belt,slurry pump, that allow for the removal of precipitate from one or moreof the following: the contacting reactor, precipitation reactor, dryingstation, or from the refining station. In certain embodiments, thesystem may further include a station for preparing a building material,such as cement, from the precipitate. This station can be configured toproduce a variety of cements, aggregates, or cementitious materials fromthe precipitate, such as described herein.

In some embodiments, the system includes a processing station that mayinclude a compressor configured to pressurize the flue gas or the sourceof carbon dioxide, the source of alkaline earth metal ions, the reactionmixture in the reactor, the precipitate, the dewatered precipitateand/or the dried precipitate, as desired. Compressors of the inventionmay employ any convenient compression protocol, and may include, but notlimited to, positive displacement pumps (e.g., piston or gear pumps),static or dynamic fluid compression pumps, radial flow centrifugal-typecompressors, helical blade-type compressors, rotary compressors,reciprocating compressors, liquid-ring compressors, among other devicesfor fluid compression. In some embodiments, the compressor may beconfigured to pressurize to a pressure of 5 atm or greater, such as 10atm or greater, such as 25 atm or greater, including 50 atm or greater.

In some embodiments, the systems may include a control station,configured to control the amount of the carbon dioxide or the carbondioxide solution and/or the amount of alkaline earth metal ions and/orthe amount of the stabilizer conveyed to the precipitator or thecharger; the amount of the precipitate conveyed to the separator; theamount of the precipitate conveyed to the drying station; and/or theamount of the precipitate conveyed to the refining station. A controlstation may include a set of valves or multi-valve systems which aremanually, mechanically or digitally controlled, or may employ any otherconvenient flow regulator protocol. In some instances, the controlstation may include a computer interface, (where regulation iscomputer-assisted or is entirely controlled by computer) configured toprovide a user with input and output parameters to control the amount,as described above.

As indicated above, the system may be present on land or sea. Forexample, the system may be a land based system that is in a coastalregion, e.g., close to a source of sea water, or even an interiorlocation, where water is piped into the system from a salt water source,e.g., ocean. Alternatively, the system may be a water based system,e.g., a system that is present on or in water. Such a system may bepresent on a boat, ocean based platform etc., as desired.

It is to be understood that the methods and the systems depicted in thefigures are in no way limiting to the scope of the invention. One ormore the steps in the methods may be skipped or the order of the stepsmay be altered to make the products and compositions of the invention.Similarly, one or more of the components in the systems may be avoidedto make the products and compositions of the invention. For example, thesource of cation may already be present in the reactor when the CO₂source is added to the reactor, or vice versa.

III. Methods and Systems of Making a Product

Aspects of the invention also provide methods and systems for making acement product from the compositions provided herein. The compositionsprovided herein may be used to make cement products such as buildingmaterials or pre-cast or formed building materials, and/or aggregates.

In one aspect, there is provided a method for making a cement productfrom the composition provided herein, including (a) combining thecomposition of the invention with an aqueous medium under one or moresuitable conditions; and (b) allowing the composition to set and hardeninto a cement product.

In some embodiments, there is provided a method of making a product,comprising (a) contacting CO₂ from a CO₂ source with a proton removingagent to form a solution; (b) contacting the solution with an alkalineearth-metal and stabilizer containing water under one or more conditionsto make a composition comprising a metastable carbonate and stabilizer;(c) combining the composition with an aqueous medium; and (d) allowingthe composition to set and harden into a cement product. In someembodiments, there is provided a method of making a product, comprising(a) contacting CO₂ from a CO₂ source with a proton removing agent toform a solution; (b) contacting the solution with an alkalineearth-metal and stabilizer containing water under one or more conditionsto make a composition comprising vaterite and stabilizer; (c) activatingthe composition comprising vaterite; (d) combining the composition withan aqueous medium; and (e) allowing the composition to set and hardeninto a cement product. In some embodiments, the composition aftersetting and hardening transforms vaterite to aragonite. In someembodiments, the methods include addition of Portland cement clinker,aggregate, SCM, or a combination thereof to the composition, beforecombining the composition with the aqueous medium.

In one aspect, there is provided a method for making formed buildingmaterial from the compositions provided herein, such as, the hydrauliccement composition, the SCM composition, or the self-cementingcomposition, by combining the composition with an aqueous medium underone or more suitable conditions; and allowing the composition to set andharden into the formed building material. In some embodiments, thecomposition is poured into molds before or after combining thecomposition with water. In some embodiments, the mold is for the formedbuilding material. In some embodiments, the aqueous medium includesfresh water.

In some embodiments, there is provided a method of producing a cementproduct from the composition provided herein by obtaining thecomposition; and producing a cement product. In some embodiments theobtaining step comprises precipitating the composition from a divalentcation-containing water, e.g., an alkaline-earth-metal-ion containingwater such as salt water, e.g., sea water. The obtaining step mayfurther comprise contacting the divalent cation-containing water, e.g.,alkaline-earth-metal-ion containing water, to an industrial gaseouswaste stream including CO₂ or a solution containing CO₂ prior to, and/orduring, the precipitating step. The industrial gaseous waste stream maybe any stream as described herein, such as from a power plant, foundry,cement plant, refinery, or smelter, e.g. a flue gas. In some embodimentsthe obtaining step further comprises raising the pH of thealkaline-earth-metal-ion containing water to 10 or higher prior to orduring the precipitating step. The producing step may include allowingthe composition to form a solid product, such as by mixing thecomposition with an aqueous medium including, but not limited to, one ormore of fresh water, Portland cement, fly ash, lime and a binder, andoptionally mechanically refining the solid product, such as by molding,extruding, pelletizing or crushing. The producing step may includecontacting the composition with fresh water to convert the polymorphs inthe composition to a freshwater stable product. In some embodiments,this may be done by spreading the composition in an open area; andcontacting the spread composition with fresh water.

In some embodiments, the aggregate producer comprises a refining stationto mechanically refine the aggregate made from the composition providedherein.

In some embodiments, the composition provided herein after mixing in thewater is poured into the molds designed to make one or more of thepre-formed building material. The composition is then allowed to set andharden into the pre-formed or pre-cast material.

In some embodiments, the composition provided herein, as prepared by themethods described above, is treated with the aqueous medium under one ormore suitable conditions. The aqueous medium includes, but is notlimited to, fresh water optionally containing sodium chloride, calciumchloride, magnesium chloride, or combination thereof or aqueous mediummay be brine. In some embodiments, aqueous medium is fresh water.

In some embodiments, the one or more suitable conditions include, butare not limited to, temperature, pH, pressure, time period for setting,a ratio of the aqueous medium to the composition, and combinationthereof. The temperature may be related to the temperature of theaqueous medium. In some embodiments, the temperature is in a range of0-110° C.; or 0-80° C.; or 0-60° C.; or 0-40° C.; or 25-100° C.; or25-75° C.; or 25-50° C.; or 37-100° C.; or 37-60° C.; or 40-100° C.; or40-60° C.; or 50-100° C.; or 50-80° C.; or 60-100° C.; or 60-80° C.; or80-100° C. In some embodiments, the pressure is atmospheric pressure orabove atm. pressure. In some embodiments, the time period for settingthe cement product is 30 min. to 48 hrs; or 30 min. to 24 hrs; or 30min. to 12 hrs; or 30 min. to 8 hrs; or 30 min. to 4 hrs; or 30 min. to2 hrs; 2 to 48 hrs; or 2 to 24 hrs; or 2 to 12 hrs; or 2 to 8 hrs; or 2to 4 hrs; 5 to 48 hrs; or 5 to 24 hrs; or 5 to 12 hrs; or 5 to 8 hrs; or5 to 4 hrs; or 5 to 2 hrs; 10 to 48 hrs; or 10 to 24 hrs; or 24 to 48hrs.

In some embodiments, the ratio of the aqueous medium to the drycomponents or to the composition of the invention (aqueous medium:drycomponents or aqueous medium:composition of the invention) is 0.1-10; or0.1-8; or 0.1-6; or 0.1-4; or 0.1-2; or 0.1-1; or 0.2-10; or 0.2-8; or0.2-6; or 0.2-4; or 0.2-2; or 0.2-1; or 0.3-10; or 0.3-8; or 0.3-6; or0.3-4; or 0.3-2; or 0.3-1; or 0.4-10; or 0.4-8; or 0.4-6; or 0.4-4; or0.4-2; or 0.4-1; or 0.5-10; or 0.5-8; or 0.5-6; or 0.5-4; or 0.5-2; or0.5-1; or 0.6-10; or 0.6-8; or 0.6-6; or 0.6-4; or 0.6-2; or 0.6-1; or0.8-10; or 0.8-8; or 0.8-6; or 0.8-4; or 0.8-2; or 0.8-1; or 1-10; or1-8; or 1-6; or 1-4; or 1-2; or 1:1; or 2:1; or 3:1.

In some embodiments, the precipitate may be rinsed with fresh water toremove halite or the chloride content from the precipitate. The chloridemay be undesirable in some applications, for example, in aggregatesintended for use in concrete since the chloride has a tendency tocorrode rebar.

In some embodiments, such rinsing may not be desirable as it may reducethe yield of the composition. In such embodiments, the precipitate maybe washed with a solution having a low chloride concentration but highconcentration of divalent cations (such as, calcium, magnesium, etc.).Such high concentration of the divalent ion may prevent the dissolutionof the precipitate, thereby reducing the yield loss and the conversionto cemented material.

During the mixing of the composition with the aqueous medium, theprecipitate may be subjected to high shear mixer. After mixing, theprecipitate may be dewatered again and placed in pre-formed molds tomake formed building materials. Alternatively, the precipitate may bemixed with water and is allowed to set. The precipitate sets over aperiod of days and is then placed in the oven for drying, e.g., at 40°C., or from 40° C.-60° C., or from 40° C.-50° C., or from 40° C.-100°C., or from 50° C.-60° C., or from 50° C.-80° C., or from 50° C.-100°C., or from 60° C.-80° C., or from 60° C.-100° C. The precipitate isthen subjected to curing at high temperature, such as, from 50° C.-60°C., or from 50° C.-80° C., or from 50° C.-100° C., or from 60° C.-80°C., or from 60° C.-100° C., or 60° C., or 80° C.-100° C., in highhumidity, such as, in 30%, or 40%, or 50%, or 60% humidity.

The cement product produced by the methods described above may be anaggregate or building material or a pre-cast material or a formedbuilding material. These materials have been described herein.

In yet another aspect, there is provided a system for making the cementproduct from the composition provided herein including (a) an input forthe composition provided herein; (b) an input for an aqueous medium; and(c) a reactor connected to the inputs of step (a) and step (b)configured to mix the composition provided herein with the aqueousmedium under one or more of suitable conditions to make a cementproduct. In some embodiments, the system further comprises a filtrationelement to filter the composition after the mixing step (c). In stillsome embodiments, the system further comprises a drying step to dry thefiltered composition to make the cement product.

FIG. 4 shows an illustrative system embodiment 200 to make the cementproduct from the composition provided herein. In some embodiments,system 200 includes a source for the composition provided herein 210. Insome embodiments, the source for the composition includes a structurehaving an input for the composition. Such structure having an inputincludes, but is not limited to, a funnel, a tube, a pipe or a conduit,etc. Any input that can facilitate the administration of the compositionto the reactor 230 is within the scope of the invention. It is wellunderstood that in some embodiments, no such source for the compositionor the structure with an input for the composition is needed, when thecomposition is already present in the reactor 230. In some embodiments,there is provided a source for aqueous medium 220 such as, wateroptionally containing sodium chloride, calcium chloride, magnesiumchloride, or combination thereof or brine. In some embodiments, thesource for the aqueous medium 220 contains an input for the aqueousmedium, such as, but not limited to, a funnel, a tube, a pipe or aconduit, etc. Any input that can facilitate the administration of theaqueous medium to the reactor 230 is within the scope of the invention.It is well understood that in some embodiments, no such source for theaqueous medium or the structure with an input for the aqueous medium isneeded, when the aqueous medium is already present in the reactor 230.

The reactor 230 is connected to the two inputs and is configured to mixthe composition with the aqueous medium under one or more of suitableconditions to make a cement product. The one or more suitable conditionshave been defined above. The reactor 230 may be configured to includeany number of different elements, such as temperature regulators (e.g.,configured to heat the water to a desired temperature), chemicaladditive elements, e.g., for introducing chemical pH elevating agents(such as NaOH) into the water. This reactor 230 may operate as a batchprocess or a continuous process. The system may optionally contain afiltration element to filter the composition after wetting (not shown inFIG. 4).

After the addition of water to the composition in the reactor, thecomposition sets and hardens into the cement product. The cement productmay optionally be dried and cured.

In one aspect, there is provided a method to make a cementitiouscomposition with desired stability of the metastable carbonate,including a) contacting CO₂ with a proton removing agent to form asolution; b) contacting the solution with alkaline earth metal ions toform a carbonate precipitate; and c) contacting a stabilizer at one ormore steps selected from the group consisting of contacting with thesolution before step b), contacting with the alkaline earth metal ionsbefore contacting with the solution; contacting with the alkaline earthmetal ions after contacting with the solution; and contacting with thecarbonate precipitate. In some embodiments, the amount of stabilizer isbetween 0.1-5% w/w. In some embodiments, the optimization of the amountof the stabilizer result sin the optimization of the stability of themetastable carbonate. In some embodiments, the optimization of theamount of the stabilizer results in the optimization of the stability ofthe metastable carbonate. In some embodiments, the optimization of thestep at which the stabilizer is added results in the optimization of thestability of the metastable carbonate.

IV. Packages

In one aspect, there is provided a package including the compositionprovided herein. In some embodiments, there is provided a packageincluding a pre-cast or a formed building material formed from thecomposition provided herein. These pre-cast or formed building materialsare as described herein. The package further includes a packagingmaterial that is adapted to contain the composition. The package maycontain one or more of such packaging materials. The packaging materialincludes, but is not limited to, metal container; sacks; bags such as,but not limited to, paper bags or plastic bags; boxes; silo such as, butnot limited to, tower silo, bunker silo, bag silo, low level mobilesilo, or static upright cement silo; and bins. It is understood that anycontainer that can be used for carrying or storing the compositionprovided herein is well within the scope of the invention.

In some embodiments, these packages are portable. In some embodiments,these packages and/or packaging materials are disposable or recyclable.

The packaging material are further adapted to store and/or preserve thecomposition provided herein for longer than few months to few years. Insome embodiments, the packaging materials are further adapted to storeand/or preserve the composition of the invention for longer than 1 week,or longer than 1 month, or longer than 2 months, or longer than 5months, or longer than 1 year, or longer than 2 years, or longer than 5years, or longer than 10 years, or between 1 week to 1 year, or between1 month to 1 year, or between 1 month to 5 years, or between 1 week to10 years.

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how tomake and use the present invention, and are not intended to limit thescope of what the inventors regard as their invention nor are theyintended to represent that the experiments below are all or the onlyexperiments performed. Efforts have been made to ensure accuracy withrespect to numbers used (e.g. amounts, temperature, etc.) but someexperimental errors and deviations should be accounted for. Unlessindicated otherwise, parts are parts by weight, molecular weight isweight average molecular weight, temperature is in degrees Centigrade,and pressure is at or near atmospheric.

EXAMPLES Example 1 Stabilizing the Composition in the Presence ofStabilizer

This example is related to the study of the stability of the compositionin the presence of a stabilizer, such as, sulfate. In this study, foursamples of the cementitious composition were taken, sample A, sample B,sample C, and sample D. All the samples were prepared using a carbondioxide solution formed by passing a gaseous stream of carbon dioxide ina solution containing a proton removing agent, such as sodium hydroxide.The carbon dioxide charged solution was then contacted with the solutioncontaining alkaline earth metal ions. Sample A was prepared from seawater with added calcium chloride to it. Sample B was prepared frommunicipal water with added calcium chloride to it. Sample C was preparedfrom water containing calcium chloride and sodium sulfate where thesulfate ions were 1000 ppm, calcium ions were 8000 ppm and magnesiumions were 70 ppm. Sample D was prepared from water containing calciumchloride and sodium sulfate where the sulfate ions were 800 ppm, calciumions were 15,000 ppm and magnesium ions were 15 ppm. Sample A was foundto be reactive; sample B was found to be stable; sample C was found tobe super stable; and sample D was found to be semi-stable. The stabilityof the samples was determined based on preliminary screening resultsincluding testing for phase transformation and scanning electronmicroscopy (SEM) images.

Experiment 1:

In this experiment, the four samples were subjected to leaching as wellas digestion experiments. In the leaching process, 100 mg of the samplewas mixed with 100 mL of DI water. The suspension was shaken for 10mins. The solid was then filtered with 0.2 μm paper and the filtrate wasanalyzed with IC (ion chromatography) for sulfate content. In thedigestion process, 100 mg of the sample was mixed with 1.5 mL of methanesulfonic acid (MSA). The solution was brought to 100 mL with DI water.The solid was then filtered with 0.2 μm paper and the filtrate wasanalyzed with IC (ion chromatography) for sulfate content. FIG. 5illustrates the amount of sulfate found in the filtrate after theleaching (A1 for sample A; B1 for sample B; C1 for sample C; and D1 forsample D) and the digestion process (A2 for sample A; B2 for sample B;C2 for sample C; and D2 for sample D) for all the four samples. Sample Awhich was a reactive sample was found to have minimum amount of sulfatecontent in the filtrate (A1 and A2). Sample B (stable), sample C (superstable) and sample D (semi-stable) were found to have higher content ofsulfate in the filtrate with the super stable sample C being the highest(C1 and C2). This study shows that there is a correlation between thecontent of the sulfate in the sample and the stability of the sample.

Experiment 2:

In this experiment, all the four samples were mixed with water and werekept at 40° C. for 7 days. All the four samples were analyzed for phasetransformation at 1 day, 3 days, and 7 days period. FIG. 6 illustratesthat the sample C which was the super stable sample showed notransformation, whereas the reactive sample A consistently transformedduring 7 day period. Sample D, however, transformed to calcite. Thisstudy shows that the sample with highest sulfate content (as shown inExperiment 1) shows super stability with no transformation and thesample with lowest sulfate content shows maximum transformation.Therefore, the amount of the stabilizer present in the compositionaffects the degree of stability of the metastable form in thecomposition.

Experiment 3:

In this experiment, sample B was treated with 0.5% gypsum (CaSO₄) whichacts as a stabilizer and with 0.5% magnesium chloride (MgCl₂). FIG. 7illustrates the effect of the stabilizer on the phase transformation ofsample B over a period of 7 days. The white bar is the control sample Bwithout gypsum or MgCl₂ added to it. FIG. 7 shows that gypsum (i.e.sulfate ions) prevents the phase transformation in sample B as comparedto magnesium chloride. Therefore, the study shows that the stabilizercan affect the stability of the metastable form in the composition.

Experiment 4:

In this experiment, sample B was treated with varying amounts of calciumsulfate (CaSO₄) to study the dissolution of calcium carbonate at roomtemperature. As described herein, the dissolution of calcium carbonateand re-precipitation leads to phase transformation. FIG. 8 shows that asthe amount of calcium sulfate was increased, the dissolution of calciumcarbonate decreased. This study further demonstrates that the stabilizerand the amount of the stabilizer can affect the stability of thepolymorphic form of the carbonate in the composition.

Example 2 Effect of Ca:CO₃ Ratio on the Stabilizer

This example is related to the study of the effect of Ca:CO₃ ratio onthe stabilizer for stabilizing the metastable carbonate in thecomposition. In this experiment, various concentrations of calciumcompound and carbonate compound were used to from calcium carbonateprecipitate with varying Ca:CO₃ ratio. The amount of sodium sulfate wasalso varied to study the effect of sulfate on the stability of vateriteformed in the composition. In addition, 10 mM magnesium was added in allthe experiments. The precipitate was vacuum filtered and dried at 60° C.The precipitate was analyzed using XRD, SEM etc. Table II illustratesparameters for such experiments and the % of vaterite formed. Theresults demonstrate that in general, as the molar ratio of Ca:CO₃increased and as the amount of stabilizer increased, the amount ofmetastable phase, i.e. vaterite, in the precipitate also increased.

TABLE II Ca:CO₃ SO₄ conc. (molar ratio) (mM) % V 1.1 2 59.8 1.3 2 66.81.6 2 82.5 1.1 4 47.9 1.3 4 92.8 1.6 4 91.6 1.1 8 99.7 1.3 8 60.7 1.6 889.7 1.1 16 97.7 1.3 16 99.2 1.6 16 77.7

It was also found that the molar ratio of calcium to carbonate mayinfluence the partitioning of sulfate into the bulk solid or into thecementitious composition. FIG. 9 illustrates that while sulfateconcentration itself does not have a strong influence on thepartitioning coefficient of sulfate, the variation in Ca:CO₃ doesinfluence partitioning coefficient of sulfate. The partition coefficient(D_(SO4)) was found to positively correlate with the excess of calciumin the precipitations.

Example 3 Nuclei Activation of Vaterite by Seeding

In this experiment, two samples of vaterite were used as controls aswell as for nuclei activation, such as seeding of vaterite witharagonite. Sample “reactive” vaterite contained about 85% vaterite andthe remaining as calcite. The sample “reactive” was prepared from seawater and the carbon dioxide solution (absorbing flue gas in sodiumhydroxide solution). Sample “stable” vaterite contained about 85%vaterite and the remaining as calcite. The sample “stable” vaterite wasprepared from process water and the carbon dioxide solution (absorbingflue gas in sodium hydroxide solution). The “reactive vaterite”transformed readily to aragonite upon dissolution-reprecipitationprocess whereas the “stable vaterite” did not significantly transform toaragonite upon dissolution-reprecipitation in water. The “stable” andthe “reactive” samples were used as controls.

The “stable” vaterite sample was mixed with 3% aragonite from threedifferent sources. In one case, the aragonite was obtained from reefsand containing about 60-70% aragonite. In second case, the aragonitewas obtained by mixing sodium carbonate with calcium chloride at 40-50°C. that resulted in aragonite precipitate (“precipitated aragonite” inFIG. 10). In the third case, the aragonite was obtained by grounding thearagonite mass formed by transformation of vaterite (“aragonite fromreactive” in FIG. 10).

To the “stable” sample with aragonite from three different sources, wasadded water in 0.6 water/solid (w/s) ratio. The paste was cured at 40°C. FIG. 10 illustrates the transformation of “reactive” vaterite;“stable” vaterite; and “stable” vaterite mixed with three differentaragonitic seeds, to aragonite over a period of 1-7 days. FIG. 10 showsthat while the control “stable” vaterite did not show significanttransformation to aragonite over a period of 7 days, the “stable”vaterite when seeded with “precipitated aragonite” or “aragonite fromreactive” or “aragonite from reef sand”, transformed to aragonite afterdissolution-reprecipitation process (comparable to “reactive” vateritesample alone).

Example 4 Thermal Activation of Vaterite

In this experiment, the “stable” and “reactive” vaterite samples ofExample 3 were used as controls in the experiment for conducting athermal activation of the vaterite sample. The “stable” vaterite samplewas mixed with water at 0.6 w/s ratio and was immediately kept in ovenat 110° C. for 1 hr. After 1 hr the sample was kept at 40° C. for 7days. The control samples, “stable” and “reactive” vaterite samples,were mixed with water in the same ratio and were kept at 40° C. for thesame time period. FIG. 11 illustrates the transformation of the twocontrol samples and the heat activated “stable” vaterite sample. FIG. 11shows that the heat activated “stable” vaterite sample showedaccelerated transformation to aragonite as compared to control “stable”vaterite sample. It is contemplated that high temperature may result inaragonite seeding in the paste which may lead to accelerated aragoniteformation upon cementation.

Example 5 Chemical Activation of Vaterite

In this experiment, the “stable” vaterite sample of Example 3 wasscreened with chemicals shown in FIG. 12. The chemical added to the“stable” vaterite sample was in 0.0005-0.5% by weight. The sample mixedwith the chemical was then mixed with water in 1:1 w/s ratio. The pastewas allowed to cure at 60° C., 100% RH chamber and tested at 1, 3, and 7days for phase composition using X-Ray diffraction and microstructuredevelopment using scanning electron microscopy. The results werecompared to the results of the vaterite material mixed with ultra-purewater. FIG. 13 shows that some chemicals (shown in two boxes) resultedin accelerated transformation of vaterite to aragonite and morphologymodification such as thinner needle aspect ratio of aragonite crystals(leading to better cross linking and compressive strength). Table IIIshows that phthalic acid (>0.5 wt %), L-aspartic acid (>0.5 wt %),L-glutamic acid (>0.5 wt %), and citric acid (>0.05 wt %) acted asstabilizers and stabilized and inhibited the vaterite material (V) fromtransforming to aragonite (A). The calcite is shown as C in the table.Table IV shows that MgCl₂ (>0.05 wt %) and PVP (>0.0005 wt %) acted asactivators and accelerated the transformation of vaterite to aragonite,forming more aragonite (20-40% at 3 days) at early-age compared toultra-pure water (−15% at 3 days).

TABLE III 1-Day 3-Day 7-Day Mix solution % V % A % C % V % A % C % V % A% C Baseline (Ultra-Pure Water) 80 3.1 16.9 68.9 12.8 18.4 32.5 48.219.3 Phthalic Acid (0.05% in DI) 84.9 0 15.1 74.4 8.5 17.1 48.7 33.218.2 Phthalic Acid (0.5% in DI) 87.5 0 12.5 87.7 0 12.3 86.5 2.1 11.4Phthalic Acid (3% in DI) 87.9 0 12.1 87.7 0 12.3 87 0 13 L-Aspartic Acid(0.05% in DI) 83.6 1.9 14.5 76.7 6.4 16.9 N/A N/A N/A L-Aspartic Acid(0.5% in DI) 87.7 0 12.3 86.9 0 13.1 N/A N/A N/A L-Aspartic Acid (3% inDI) 88.4 0 11.6 87 0 13 N/A N/A N/A L-Glutamic Acid (0.05% in DI) 85.1 014.9 80.4 0 19.6 71.8 9.1 19.1 L-Glutamic Acid (0.5% in DI) 87.7 0 12.386.3 0 13.7 86 0 14 L-Glutamic Acid (3% in DI) 87.3 0 12.7 85.4 0 14.687.9 0 12.1 Citric Acid (0.0005% in DI) 81.9 2.3 15.8 64.2 16.1 19.816.4 60.8 22.8 Citric Acid (0.005% in DI) 82.8 0 17.2 71.9 6.7 21.4 49.827.6 22.6 Citric Acid (0.05% in DI) 83.1 1.4 15.5 77.5 0 22.5 71.7 028.3 Citric Acid (0.5% in DI) 86.5 0 13.5 86.7 0.5 12.8 85.6 0 14.4

TABLE IV 1-Day 3-Day 7-Day % V % A % C % V % A % C % V % A % C Baseline(Ultra-Pure 80 3.1 16.9 68.9 12.8 18.4 32.5 48.2 19.3 Water) MgCl2(0.0005% in DI) 79.8 3.6 16.6 66 15.9 18.1 15.9 61.2 21.6 MgCl2 (0.005%in DI) 80.2 3.9 15.9 67.2 15.1 17.8 20.2 58.5 20.7 MgCl2 (0.05% in DI)81.7 3.6 14.6 62.9 21.5 15.5 4.5 76.2 18.5 MgCl2 (0.5% in DI) 80.2 6.313.5 47 39.2 13.8 2.4 80.5 15.7 Poly (N-vinyl-1-pyrrolidine) 78.6 5.4 1655.9 27.5 16.5 3.6 76.8 19.6 (0.0005% in DI) Poly(N-vinyl-1-pyrrolidine) 78.4 7 14.6 52.8 32.9 14.3 2.8 79.2 18 (0.005%in DI) Poly (N-vinyl-1-pyrrolidine) 80.5 3.5 16.1 64.5 18.2 17.3 14.664.8 20.6 (0.05% in DI) Poly (N-vinyl-1-pyrrolidine) 79.1 4.9 16 57.3 2715.7 5 76.7 18.4 (0.5% in DI)

Example 6 Mechanical Activation of Vaterite

In this experiment, the “stable” and “reactive” vaterite samples, asdescribed in Example 3, were used as controls and three “stable” sampleswere ball-milled for different periods of time to study the effect ofmechanical activation, such as ball-milling. The samples were mixed withwater at 0.6 w/s ratio and were kept at 40° C. FIG. 14 illustrates thecalcium dissolution study of the samples where the “stable” sample thatwas ball-milled for maximum period of time, i.e. 72 hr, showed maximumdissolution of calcium. FIG. 15 shows that the ball-milled samplestransformed to aragonite readily (even better than “reactive” sample)whereas the “stable” sample that was not ball-milled didn't show anysignificant aragonite formation.

Example 7 Measurement of δ¹³C Value for Precipitation Material

In this experiment, carbonate-containing precipitation material isprepared using a mixture of bottled sulfur dioxide (SO₂) and bottledcarbon dioxide (CO₂) gases, NaOH as a source of alkalinity, and calciumchloride as a source of divalent cations. The procedure is conducted ina closed container. The starting materials are a mixture of commerciallyavailable bottled SO₂ and CO₂ gas (SO₂/CO₂ gas or “simulated flue gas”).A container is filled with de-ionized water. Sodium hydroxide andcalcium chloride are added to it providing a pH (alkaline) and divalentcation concentration suitable for precipitation of carbonate-containingprecipitation material containing vaterite without releasing CO₂ intothe atmosphere. SO₂/CO₂ gas is sparged at a rate and time suitable toprecipitate precipitation material from the alkaline solution.Sufficient time is allowed for interaction of the components of thereaction, after which the precipitation material is separated from theremaining solution (“precipitation reaction mixture”), resulting in wetprecipitation material and supernatant.

δ¹³C values for the process starting materials, precipitation material,and supernatant are measured. The analytical system used is manufacturedby Los Gatos Research and uses direct absorption spectroscopy to provideδ¹³C and concentration data for dry gases ranging from 2% to 20% CO₂.The instrument is calibrated using standard 5% CO₂ gases with knownisotopic composition, and measurements of CO₂ evolved from samples oftravertine and IAEA marble #20 digested in 2M perchloric acid yieldvalues that are within acceptable measurement error of the values foundin literature. The CO₂ source gas is sampled using a syringe. The CO₂gas is passed through a gas dryer (Perma Pure MD Gas Dryer, ModelMD-110-48F-4 made of Nafion® polymer), then into the bench-topcommercially available carbon isotope analytical system. Solid samplesare first digested with heated perchloric acid (2M HClO₄). CO₂ gas isevolved from the closed digestion system, and then passed into the gasdryer. From there, the gas is collected and injected into the analysissystem, resulting in δ¹³C data. Similarly, the supernatant is digestedto evolve CO₂ gas that is then dried and passed to the analysisinstrument resulting in δ¹³C data.

The δ¹³C values for the precipitation material are found to be less than−15‰. This Example illustrates that δ¹³C values can be used to confirmthe primary source of carbon in a carbonate-containing precipitationmaterial.

Example 8 Vaterite Stabilization with Sulfate Addition

A hard brine solution was prepared by diluting concentrated CaCl₂ to0.355 mol/L and subsequently Na₂SO₄ was dissolved to a concentration of0.0061 mol/L in the hard brine solution. An alkaline brine was preparedby absorbing CO₂ into a 1.382 mol/L NaOH solution, until the pH isbetween 10-11. The two solutions were mixed flowed into a mixed tank atrates of 8.17 gpm of hard brine solution and 3.88 gpm of alkalinesolution. The precipitated slurry was pumped out of the bottom of thetank at a rate that maintained a constant volume of 70 gallons in thetank (average liquid residence time in the tank was 5.8 min). The slurrywas allowed to gravity settle, while continuously decanting. Theconcentrated slurry was then filter pressed and subsequently dried in aswirl fluidized dryer. The dry composition showed particle sizedistribution of 18.124 μm mean diameter (standard deviation of 6.178 μm)determined by a static light scattering technique. The mineralogyanalysis of the composition showed 86.8% vaterite, 0.6 wt % sulfate, and13.2% calcite determined by powder x-ray diffraction, and quantifiedusing Rietveld refinement.

The dry vaterite composition was mixed with water to form a paste. Threemixes, namely, 100% composition; mortar (27% composition and 73% quartzsand), and concrete (20% composition and 80% quartz sand and rocks) weremixed with an ionic solution at a water-to-cement ratio of 0.4 in aHobart mixer for 5 mins. The mixed materials were then cast into 2-incube molds and cured in a 60° C., 100% RH chamber for 1 day. At 1 day ofreaction, the test cubes were demolded and placed in a ionic solutionbath at 60° C. for 6 days. At 7 day of reaction, the test cubes weredried in a 100° C. oven for 6 hours then tested for compressionstrength. The three mixes achieved a compressive strength of 4600 psi inpaste with 100% composition, 3700 psi in mortar, and 4200 psi inconcrete.

Example 9 Rinsing with Chemical Additives

In this experiment, the filter pressed cake obtained by the processdescribed in Example 8, was rinsed with 1.5M sodium carbonate solution.FIG. 16 illustrates the % sulfate content in the two of the digestedsamples of the filter pressed cake without sodium carbonate rinse andwith 1.5M sodium carbonate rinse. The sulfate content in both thesamples of the cake was found to be reduced by about 50% after rinsingwith sodium carbonate. It is contemplated that the carbonate-sulfate ionexchange may be taking place at the surface of the vaterite particles.

In a second experiment, the filter pressed cake obtained by the processdescribed in Example 8, was rinsed with 1.5M sodium carbonate solutionand 1.4M magnesium chloride solution in sequence. Five samples of thefilter pressed cakes were subjected to five different sequences. Thesequence C-M-W was carbonate rinse, followed by magnesium chloriderinse, followed by water rinse. The sequence C—W was carbonate rinsefollowed by water rinse. The sequence W was just water rinse. Thesequence W—C was water rinse followed by carbonate rinse. The sequenceW—C-M was water rinse, followed by carbonate rinse, followed bymagnesium chloride rinse. As illustrated in FIG. 17A, while thesequences C—W, W, and W—C showed small % of magnesium in the digestedsample (may be due to magnesium present in raw materials or water duringprecipitation process), the sequences C-M-W and W—C-M showed higheramount of magnesium uptake by the precipitate. It is contemplated thatthe highest amount of magnesium in W—C-M sequence could be due to lastrinsing with magnesium chloride solution with no subsequent waterrinsing.

All the five sample precipitates were subsequently dried. The driedsamples were subjected to paste formation with DI water (0% MgCl₂ shownas I in FIG. 17B) or with water containing 0.5% MgCl₂ (shown as II inFIG. 17B). FIG. 17B illustrates the 1-day % aragonite conversion of thevaterite in the paste made from five samples described in FIG. 17A. Theprecipitate rinsed with sequences C—W, W, and W—C showed minimalconversion of vaterite to aragonite (illustrated as A for both I and IIin FIG. 17B). The precipitate rinsed with sequence C-M-W showed moderateconversion of vaterite to aragonite (illustrated as B for both I and IIin FIG. 17B). The precipitate rinsed with sequence W—C-M showed highestconversion of vaterite to aragonite (illustrated as C for both I and IIin FIG. 17B). The results showed similar comversion in the pastes madewith DI water (0% MgCl₂) or with water containing 0.5% MgCl₂. Theresults show that the aragonite development in paste screening wasdependent on the magnesium ion concentration in the vaterite particlesor on the surface of the vaterite particles and was relativelyindependent of the paste water composition (% MgCl₂ in paste water).

1-42. (canceled)
 43. A method for making a composition, comprising:making a composition comprising at least 50% w/w activated vaterite;activating the composition by adding one or more of aragonite seed,inorganic additive or organic additive; combining the composition withwater and facilitating vaterite transformation to aragonite when thecomposition sets and hardens to form cement.
 44. The method of claim 43,wherein the inorganic additive or the organic additive are selected fromthe group consisting of sodium decyl sulfate, lauric acid, sodium saltof lauric acid, urea, citric acid, sodium salt of citric acid, phthalicacid, sodium salt of phthalic acid, taurine, creatine, dextrose,poly(n-vinyl-1-pyrrolidine), aspartic acid, sodium salt of asparticacid, magnesium chloride, acetic acid, sodium salt of acetic acid,glutamic acid, sodium salt of glutamic acid, strontium chloride, gypsum,lithium chloride, sodium chloride, glycine, sodium citrate dehydrate,sodium bicarbonate, magnesium sulfate, magnesium acetate, sodiumpolystyrene, sodium dodecylsulfonate, poly-vinyl alcohol, orcombinations thereof.
 45. The method of claim 43, wherein the inorganicadditive is strontium chloride, gypsum, lithium chloride, magnesiumsulfate, magnesium acetate, magnesium chloride, or combinations thereof.46. The method of claim 43, wherein the organic additive is citric acid,sodium salt of citric acid, phthalic acid, sodium salt of phthalic acid,aspartic acid, sodium salt of aspartic acid, glutamic acid, sodium saltof glutamic acid, poly(n-vinyl-1-pyrrolidone), or combinations thereof.47. The method of claim 43, wherein the composition comprises between0.001-10% w/w aragonite seed, inorganic additive or organic additive.48. The method of claim 43, wherein the facilitating the aragoniteformation results in one or more of better linkage or bonding, highertensile strength, or higher impact fracture toughness, after cementationof the composition.
 49. The method of claim 43, wherein the compositionafter combination with water, setting and hardening has a compressivestrength in a range of 14-40 MPa.
 50. The method of claim 43, whereinthe composition is a precipitate, slurry, or a dry powder.
 51. Themethod of claim 43, wherein the cement is a formed building materialselected from the group consisting of masonry unit, brick, block, tile,construction panel, cement board, fiber-cement siding, drywall, conduit,basins, beam, column, concrete slab, acoustic barrier, insulationmaterial, and combination thereof.
 52. The method of claim 43, whereinthe composition has an average particle size of between 0.1-100 microns.53. The method of claim 43, further comprising contacting CO₂ from a CO₂source with a solution comprising proton removing agent and alkalineearth-metal ions under one or more conditions to make the composition.54. The method of claim 53, wherein the one or more conditions areselected from the group consisting of mixing, stirring, temperature, pH,precipitation, residence time of the precipitate, dewatering ofprecipitate, washing precipitate with water, ion ratio, concentration ofadditives, drying, milling, grinding, storing, aging, and curing. 55.The method of claim 53, wherein the one or more conditions comprisehaving ratio of calcium to carbonate during formation of the activatedvaterite to be between 1:1 to 1.5:1.
 56. The method of claim 43, furthercomprising activating the composition by thermal activation, mechanicalactivation, or combination thereof.
 57. The method of claim 43, whereinthe activated vaterite has relative carbon isotope composition (δ¹³C)value of less than −12‰.